Protected functionalized diene and alkenyl substituted aromatic silicone triblock copolymers and processes for making the same

ABSTRACT

Terminally functionalized silicone triblock copolymers prepared using protected functionalized initiators and processes for preparing the same. The silicone triblock copolymers includes protected, functionalized silicone diene and/or alkenylsubstituted aromatic copolymers. The protected functionalized copolymers can be optionally deprotected to afford functionalized silicone diene and/or alkenylsubstituted aromatic copolymers.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part application of copendingapplication Ser. No. 09/082,404, filed May 20, 1998, now U.S. Pat. No.6,020,430 the entire disclosure of which is hereby incorporated byreference.

FIELD OF THE INVENTION

This invention relates to novel protected functionalized diene andalkenylsubstituted aromatic/silicone triblock copolymers, theiroptionally hydrogenated analogues, their optionally deprotectedanalogues, and processes for making the same.

BACKGROUND OF THE INVENTION

Silicone polymers have many unique properties, including wide servicetemperature range; low viscosity change vs. temperature; lowflammability; shear stability; chemical inertness; oxidative stability;UV stability; low toxicity; and the like. These and other propertieshave facilitated the adoption of silicone polymers as dielectric,hydraulic, heat transfer, power transmission and damping fluids.Silicone polymers have also found applications as additives incorporatedinto plastics and rubbers as process and release aids, into coatings forflow and level control and into process streams as antifoams. Otherunique properties have led to their introduction in acousticalapplications such as ultrasonic sensor and sonar buoys. Thisproliferation of applications has engendered many improvements andrefinements of silicone polymers.

Thermoplastic elastomers typically consist of a non-compliant, highmodulus polymeric “hard segment” which is covalently bonded to a “soft”elastomeric segment comprised of polymer which is significantly aboveits glass transition temperature during use. These materials offer auseful combination of elastomeric properties without vulcanization.

Anionic polymerization of cyclosiloxanes, particularlyhexamethylcyclotrisiloxane (D₃) and octamethyltetrasiloxane (D₄), hasbeen reported previously. It is known that D₃ polymerization does notoccur in hydrocarbon solvents. See C. L. Frye, R. M. Salinger, F. W.Fearon, J. M. Klosowski and T. deYoung, J. Org. Chem., 35, 1308 (1970).Although the anionic species was formed (Bu—Si(CH₃)₂)—O—Li⁺), it did notpolymerize. Addition of a polar promoter, such as THF, diglyme, or DME,then stimulated the polymerization. See J. M. Yu, D. Teyssie, R. B.Khalife and S. Boileau, Polymer Bulletin, 32, 35-40 (1994). Theresultant polymer anion PDMS-O—Li⁺ can then be protonated to affordPDMS-OH, capped with a silicon halide (R³R⁴R⁵—Si—X) to affordPDMS-O—SiR³R⁴R⁵, or coupled with suitable coupling agents (SiCl₄,Me₂SiCl₂, HSi(OMe)₃) to afford (PDMS)_(n), where n=number of couplingagent functionalities. In spite of considerable synthetic efforts,however, there are few good ways to affix functionality to the terminiof the silicone polymers.

Conventional hydrocarbon-based polymers generally lack mechanisms forbringing about crosslinking via low-temperature or ambient temperaturecure (e.g., moisture cure or addition-cure). Such cure pathways areknown in the case of siloxane polymers, and the development of suchfacile cure mechanisms for organic systems is highly desirable.

Unfunctionalized hydrocarbon/silicone diblock copolymers have beenprepared by anionic techniques, as described in U.S. Pat. No. 5,618,903,Makromol. Chem., 176, 1641 (1975), Polym. Sci., Part B: Polym. Phys.,30, 727 (1992), Inorg. and Organomet. Polym., 1, 397 (1991), andMacromolecules, 29, 3397 (1996). Symmetrical, homotelechelic,functionalized hydrocarbon/silicone block copolymers were also preparedanionically, as detailed in U.S. Pat. No. 5,561,210. Symmetricalhomotelechelic functionalized hydrocarbon/silicon block copolymers werealso prepared anionically, as detailed in U.S. Pat. No. 5,561,210.

SUMMARY OF THE INVENTION

The present invention provides novel protected functionalizedheterotelechelic silicone block copolymers having the formula (I) or(II):

(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—H  (I);

(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR³R⁴R⁵  (II);

protected macromonomers of formula (II′):

(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR^(3′)R^(4′)R^(5′)  (II′);

protected homotelechelic copolymers of formula (III):

[(R7R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)]₂—L  (III)

in which each T—(A—R⁷R⁸R⁹)_(m) as defined below is the same;

protected heterotelechelic copolymers of the formula (III′):

[(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)]₂—L  (III′)

in which each T—(A—R⁷R⁸R⁹)_(m) as defined below is different and each C′can be the same or different;

protected heterotelechelic copolymers of the formula (III″):

(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—FG  (III″)

in which FG and T—(A—R⁷R⁸R⁹)_(m) are different; and protected radialcopolymers of the formula (IV) or (V):

[(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)]_(z)—L′  (IV)

or

[(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′]_(z)—DVB—[(R¹R²Si—O)_(v)—SiR³R⁴R⁵]_(y)  (V)

in which each T—(A—R⁷R⁸R⁹)_(m) and each C′ can be the same or different,

wherein:

Q is an unsaturated or hydrogenated hydrocarbyl group derived byincorporation of one or more conjugated diene hydrocarbons, one or morealkenylsubstituted aromatic compounds, or mixtures of one or more dieneswith one or more alkenylsubstituted aromatic compounds into the M—Zlinkage;

n is an integer from 0 to 5;

Z is a branched or straight chain hydrocarbon connecting group whichcontains 3-25 carbon atoms, optionally substituted with aryl orsubstituted aryl;

C′ is a hydrogenated or unsaturated block derived by anionicpolymerization of one or more conjugated dienes, for example1,3-butadiene or isoprene, or one or more alkenylsubstituted aromaticcompounds, such as styrene or alpha-methylstyrene, or mixtures of one ormore conjugated dienes and one or more alkenylsubstituted aromaticcompounds;

DVB is radial polymer core prepared by addition of protectedfunctionalized polymer anions to an alkenylsubstituted aromatic compoundwhich contains two or more independently polymerizable vinyl groups,such as meta-divinylbenzene or para-divinylbenzene;

T is selected from the group consisting of oxygen, sulfur, and nitrogengroups and mixtures thereof;

(A—R⁷R⁸R⁹)_(m) is a protecting group in which A is an element selectedfrom Group IVa of the Periodic Table of the Elements; R⁷, R⁸, and R⁹ areeach independently selected from the group consisting of hydrogen,alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl andsubstituted cycloalkyl or when T is nitrogen, R⁹ is optionally a—(CR′R′)_(l)-group linking two A wherein each R′ is each independentlyselected from the group consisting of hydrogen, alkyl, substitutedalkyl, aryl, substituted aryl, cycloalkyl, and substituted cycloalkyl,and 1 is an integer from 1 to 7; and m is 1 when T is oxygen or sulfur,and 2 when T is nitrogen;

R¹ and R² are each independently selected from the group consisting ofhydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl,and substituted aryl;

v is an integer from 2 to 100,000;

R³, R⁴, and R⁵ are each independently selected from the group consistingof hydrogen, alkyl, substituted alkyl, fluorinated alkyl, alkylcontaining an acetal functionality, alkenyl, substituted alkenyl, aryl,and substituted aryl;

R³, R⁴, and R⁵ are each independently selected from the group consistingof hydrogen, alkyl, substituted alkyl, fluorinated alkyl, alkylcontaining an acetal functionality, alkenyl, substituted alkenyl, aryl,substituted aryl, and free radically polymerizable groups, with theproviso that at least one of R³, R⁴, and R⁵ is a free radicallypolymerizable group;

FG is a protected or non-protected functional group;

L is a residue of a difunctional linking agent, such as a SiMe₂ residuederived from the difunctional linking agent SiMe₂Cl₂;

L′ is a residue of a multifunctional linking agent, such as a Si residuederived from the multifunctional linking agent SiCl₄; and

y and z are each independently integers from 2 to 30.

The present invention also provides novel protected mono-functionalizedtriblock silicone copolymers, such as compounds having the formula (X),(XI), or (XII):

(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—(O—SiR¹⁰R¹¹)_(w)—D—R  (X)

(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—D—R  (XI)

and

(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—SiR¹²R¹³—(O—SiR¹⁰R¹¹)_(w)—D—R  (XII)

wherein:

each Q is independently selected from an unsaturated or hydrogenatedhydrocarbyl group derived by incorporation of one or more conjugateddiene hydrocarbons, one or more alkenylsubstituted aromatic compounds,or a mixture of one or more dienes with one or more alkenylsubstitutedaromatic compounds into a M—Z linkage;

each C′ and D is independently selected from a hydrogenated orunsaturated block derived by anionic polymerization of one or moreconjugated dienes, for example 1,3-butadiene or isoprene, or one or morealkenylsubstituted aromatic compounds, such as styrene oralpha-methylstyrene, or a mixture of one or more conjugated dienes andone or more alkenylsubstituted aromatic compounds;

(A—R⁷R⁸R⁹)_(m) is a protecting group in which A is an element selectedfrom Group IVa of the Periodic Table of the Elements; R⁷, R⁸, and R⁹ areeach independently selected from the group consisting of hydrogen,alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl andsubstituted cycloalkyl or when T is nitrogen, R⁹ is optionally a—(CR′R′)₁-group linking two A wherein each R′ is each independentlyselected from the group consisting of hydrogen, alkyl, substitutedalkyl, aryl, substituted aryl, cycloalkyl, and substituted cycloalkyl,and 1 is an integer from 1 to 7; and m is 1 when T is oxygen or sulfur,and 2 when T is nitrogen;

each R¹, R², R¹⁰, R¹¹, R¹², and R¹³ is independently selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, alkenyl,substituted alkenyl, aryl, and substituted aryl;

each R is independently selected from a hydrocarbyl group of 1-20 carbonatoms derived from an unfunctionalized initiator capable of initiatingpolymerization of conjugated dienes or alkenylsubstituted aromaticcompounds; and

each w and v is independently selected from an integer from 2 to100,000.

The present invention also provides functionalized silicone copolymersand triblock silicone copolymers as described above in which at leastone protecting group —(A—R⁷R⁸R⁹)_(m) has been removed to liberate theprotected functionality T (oxygen, nitrogen, or sulfur). The functionalgroups can then optionally participate in various copolymerizationreactions by reaction of the functional groups on the ends of thecopolymer arms with selected difunctional or polyfunctional comonomersas described in more detail below to provide a silicone copolymer havingpolymer segments.

The novel copolymers can also be optionally hydrogenated to afford othernovel copolymers. The protecting groups can be removed either prior toor following this hydrogenation.

The copolymers of the invention provide facile cure mechanisms fororganic systems to allow crosslinking via low-temperature or ambienttemperature cure (e.g., moisture cure or addition-cure). Thus, forexample, a telechelic organic polymer of the invention having suitablyreactive end-groups could be reacted through chain extension and/orcrosslinking schemes to produce cured compositions having precisemolecular weight between crosslinks, and therefore, more predictable andcontrollable properties. The copolymers of the invention are also usefulas compatibilzers in polymer blends and as modifiers for pigments andfillers.

In addition, the copolymers of the invention provide advantages over theunfunctionalized hydrocarbon/silicone block copolymers described in U.S.Pat. No. 5,618,903, Makromol. Chem., 176, 1641 (1975), Polym. Sci., PartB: Polym. Phys., 30, 727 (1992), Inorg. and Organomet. Polym., 1, 397(1991), and Macromolecules, 29, 3397 (1996), referenced above. Forexample, the copolymers of the invention provide the presence ofterminal functionality on a hydrocarbon block. Further, thefunctionality on the hydrocarbon block can be readily altered by changein initiator species. Still further, a variety of heteroatoms can beincorporated into hydrocarbon block by change in the initiator, and theprotecting group can be easily removed.

The copolymers of the invention are also advantageous over thesymmetrical, homotelechelic functionalized block copolymers of U.S. Pat.No. 5,561,210. The present invention is superior to this referencebecause the functionality of each polymer chain is precisely controlled.In addition, each of the hydrocarbon polymer segments can be derivedfrom the same or different monomers and each of the hydrocarbon polymersegments can be the same or different molecular weight. Further each ofthe hydrocarbon polymer segments can be the same or differentmicrostructure.

The polymers and processes of the invention can provide otheradvantages. Typically silicone polymers are produced using traditionalequilibrium reaction approaches. Such processes, however, providelimited or no control of polymer molecular weight distribution andbyproducts. In contrast, the copolymers of the present invention can beprepared using anionic polymerization techniques. This allows productionof copolymers having a relatively narrow molecular weight distribution(M_(w)/M_(n)), typically less than or about 1.5, and fewer byproducts.

In addition, the molecular architecture of copolymers of the presentinvention can be precisely controlled. For example, the monomercomposition, length and molecular weight of the arms of multi-branchedpolymers can be independently manipulated by varying the monomer chargedto the initiator. The microstructure of the hydrocarbon segments canalso be varied. Also various protected functional groups and differentprotected heteroatoms can be introduced into the same multi-armcopolymer molecule by employing a mixture of initiators that containdifferent heteroatoms. Further, differentially protected heteroatoms canbe introduced into the same multi-arm copolymer molecule by employing amixture of initiators that contain different protecting groups.

Still further, different protecting groups can be removed sequentiallyto afford a polymer with some of the functional groups exposed, and someprotected. The newly exposed functional groups can then participate invarious copolymerization reactions, or reaction with methacroyl chlorideto afford a macromonomer. The remaining protecting groups can then beremoved, and then these functional groups can then participate infurther copolymerization reactions.

DETAILED DESCRIPTION OF THE INVENTION

The silicone copolymers of the present invention include copolymers ofthe following formulas:

protected copolymers of formulas (I) and (II):

(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—H  (I);

(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR³R⁴R⁵  (II);

protected macromonomers of formula (II′):

(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR^(3′)R^(4′)R^(5′)  (II′);

protected homotelechelic copolymers of formula (III):

[(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)]₂—L  (III)

in which each T—(A—R⁷R⁸R⁹)_(m) as defined below is the same;

protected heterotelechelic copolymers of the formula (III′):

[(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)]₂—L  (III′)

in which each T—(A—R⁷R⁸R⁹)_(m) as defined below is different and furtherin which each C′ can be the same or different;

protected heterotelechelic copolymers of the formula (III″):

(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—FG  (III″)

in which FG and T—(A—R⁷R⁸R⁹)_(m) as defined below are different; andprotected radial copolymers of the formula (IV) or (V):

[(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)]_(z)—L′  (IV)

[(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′]_(z)—DVB—[(R¹R²Si—O)_(v)—SiR³R⁴R⁵]_(y)  (V)

in which each T—(A—R⁷R⁸R⁹)_(m) and each C′ can be the same or different;

wherein:

Q is an unsaturated or hydrogenated hydrocarbyl group derived byincorporation of one or more conjugated diene hydrocarbons, one or morealkenylsubstituted aromatic compounds, or mixtures of one or more dieneswith one or more alkenylsubstituted aromatic compounds into the M—Zlinkage;

n is an integer from 0 to 5;

Z is a branched or straight chain hydrocarbon connecting group whichcontains 3-25 carbon atoms, optionally substituted with aryl orsubstituted aryl;

C′ is a hydrogenated or unsaturated block derived by anionicpolymerization of one or more conjugated dienes, for example1,3-butadiene or isoprene, or one or more alkenylsubstituted aromaticcompounds, such as styrene or alpha-methylstyrene, or mixtures of one ormore conjugated dienes and one or more alkenylsubstituted aromaticcompounds;

DVB is radial polymer core prepared by addition of protectedfunctionalized polymer anions to an alkenylsubstituted aromatic compoundwhich contains two or more independently polymerizable groups;

T is selected from the group consisting of oxygen, sulfur, and nitrogengroups and mixtures thereof;

(A—R⁷R⁸R⁹)_(m) is a protecting group in which A is an element selectedfrom Group IVa of the Periodic Table of the Elements; R⁷, R⁸, and R⁹ areeach independently selected from the group consisting of hydrogen,alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl andsubstituted cycloalkyl or when T is nitrogen, R⁹ is optionally a—(CR′R′)_(l)-group linking two A wherein each R′ is each independentlyselected from the group consisting of hydrogen, alkyl, substitutedalkyl, aryl, substituted aryl, cycloalkyl, and substituted cycloalkyl,and 1 is an integer from 1 to 7; and m is 1 when T is oxygen or sulfur,and 2 when T is nitrogen. Thus the skilled artisan will appreciate thatR⁹ as used herein includes the group

linking two A groups;

v is an integer from 2 to 100,000;

R³, R⁴, and R⁵ are each independently selected from the group consistingof hydrogen, alkyl, substituted alkyl, fluorinated alkyl, alkylcontaining an acetal functionality, alkenyl, substituted alkenyl, aryl,and substituted aryl;

R^(3′), R^(4′), and R^(5′) are each independently selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, fluorinatedalkyl, alkyl containing an acetal functionality, alkenyl, substitutedalkenyl, aryl, substituted aryl, and free radically polymerizablegroups, with the proviso that at least one of R^(3′), R^(4′), and R^(5′)is a free radically polymerizable group;

FG is a protected or non-protected functional group;

L is a residue of a difunctional linking agent, such as a SiMe₂ residuederived from the difunctional linking agent SiMe₂Cl₂;

L′ is a residue of a multifunctional linking agent, such as a Si residuederived from the multifunctional linking agent SiCl₄; and

y and z are each independently integers from 2 to 30.

The present invention also provides novel protected mono-functionalizedtriblock silicone block copolymers, including compounds having theformula (X), (XI), or (XII) as follows:

(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—(O—SiR¹⁰R¹¹)_(w)—D—R  (X)

(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—D—R  (XI)

and

(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—SiR¹²R¹³—(O—SiR¹⁰R¹¹)_(w)—D—R  (XII)

wherein:

each Q is independently selected from an unsaturated or hydrogenatedhydrocarbyl group derived by incorporation of one or more conjugateddiene hydrocarbons, one or more alkenylsubstituted aromatic compounds,or a mixture of one or more dienes with one or more alkenylsubstitutedaromatic compounds into a M—Z linkage;

each Z is independently selected from a branched or straight chainhydrocarbon connecting group which contains 3-25 carbon atoms,optionally substituted with aryl or substituted aryl;

each C′ and D is independently selected from a hydrogenated orunsaturated block derived by anionic polymerization of one or moreconjugated dienes, for example 1,3-butadiene or isoprene, or one or morealkenylsubstituted aromatic compounds, such as styrene oralpha-methylstyrene, or a mixture of one or more conjugated dienes andone or more alkenylsubstituted aromatic compounds;

each T is independently selected from the group consisting of oxygen,sulfur, and nitrogen groups and mixtures thereof;

each (A—R⁷R⁸R⁹)_(m) is independently selected from a protecting group inwhich A is an element selected from Group IVa of the Periodic Table ofthe Elements; R⁷, R⁸, and R⁹ are each independently selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, aryl,substituted aryl, cycloalkyl and substituted cycloalkyl or when T isnitrogen, R⁹ is optionally a —(CR′R′)₁-group linking two A wherein eachR′ is each independently selected from the group consisting of hydrogen,alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, andsubstituted cycloalkyl, and 1 is an integer from 1 to 7; and m is 1 whenT is oxygen or sulfur, and 2 when T is nitrogen. Thus the skilledartisan will appreciate that R⁹ as used herein includes the group

linking two A groups;

each R¹, R², R¹⁰, R¹¹, R¹², and R¹³ is independently selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, alkenyl,substituted alkenyl, aryl, and substituted aryl;

each R is independently selected from a hydrocarbyl group of 1-20 carbonatoms derived from an unfunctionalized initiator capable of initiatingpolymerization of conjugated dienes or alkenyl substituted aromaticcompounds; and

each w and v is independently selected from an integer from 2 to100,000.

The present invention provides numerous advantages over prior siliconpolymers and processes for making the same. For example, the anionicpolymerization processes of the invention can provide improved controlof copolymer molecular distribution (typically less than or about 1.5)and fewer byproducts. In addition, copolymers of the invention whichinclude two or more polymer arms or branches can include arms of varyingcomposition, length and molecular weight.

As used herein, unless otherwise indicated, the term “alkyl” refers tostraight chain and branched C1-C25 alkyl. The term “substituted alkyl”refers to C1-C25 alkyl substituted with one or more lower C1-C10 alkyl,lower alkoxy, lower alkylthio, or lower dialkylamino. The term“cycloalkyl” refers to C3-C12 cycloalkyl. The term “substitutedcycloalkyl” refers to C3-C12 cycloalkyl substituted with one or morelower C1-C10 alkyl, lower alkoxy, lower alkylthio, or lowerdialkylamino. The term “aryl” refers to C5-C25 aryl having one or morearomatic rings, each of 5 or 6 carbon atoms. Multiple aryl rings may befused, as in naphthyl or unfused, as in biphenyl. The term “substitutedaryl” refers to C5-C25 aryl substituted with one or more lower C1-C10alkyl, lower alkoxy, lower alkylthio, or lower dialkylamino. Exemplaryaryl and substituted aryl groups include, for example, phenyl, benzyl,and the like. The term “alkenyl” refers to C2-C20 alkenyl and the term“substituted alkenyl” refers to C2-C20 alkenyl substituted with one ormore lower C1-C10 alkyl, lower alkoxy, lower alkylthio, or lowerdialkylamino. The term “free radically polymerizable group” refers toethylenically unsaturated groupings, such as an omega-acrylate ormethacrylate substituted alkyl groups (such as 3-(methacryloxy)propyl),alkenyl substituted aromatic compounds (such as 4-vinylphenyl), and thelike.

The novel protected functionalized silicone copolymers of the presentinvention can be prepared as described in detail below.

Protected functionalized living polymer anions can be prepared byanionically polymerizing a conjugated diene, a mixture of conjugateddiene monomers, an alkenylsubstituted aromatic compound, a mixture ofalkenylsubstituted aromatic compounds, or a mixture of one or moreconjugated diene monomers together with one or more alkenylsubstitutedaromatic compounds in an inert solvent, optionally in the presence of apolar modifier, at a temperature from −30° C. to 150° C. for a period ofat least one hour with one or more protected functionalized initiatorshaving the formula:

M—Q_(n)—Z—T—(A—R⁷R⁸R⁹)_(m)  (VI)

or

wherein:

M is an alkali metal selected from the group consisting of lithium,sodium and potassium;

Q is an unsaturated or hydrogenated hydrocarbyl group derived byincorporation of one or more conjugated diene hydrocarbons, one or morealkenylsubstituted aromatic compounds, or mixtures of one or more dieneswith one or more alkenylsubstituted aromatic compounds into the M—Zlinkage;

n is an integer from 0 to 5;

Z is a branched or straight chain hydrocarbon connecting group whichcontains 3-25 carbon atoms, optionally substituted with aryl orsubstituted aryl;

T is selected from the group consisting of oxygen, sulfur, and nitrogengroups and mixtures thereof;

(A—R⁷R⁸R⁹)m is a protecting group in which A is an element selected fromGroup IVa of the Periodic Table of the Elements; R⁷, R⁸, and R⁹ are eachindependently selected from the group consisting of hydrogen, alkyl,substituted alkyl, aryl, substituted aryl, cycloalkyl, and substitutedcycloalkyl or as illustrated when T is nitrogen, R⁹ is optionally a—(CR′R′)₂-group linking two A wherein each R′ is each independentlyselected from the group consisting of hydrogen, alkyl, substitutedalkyl, aryl, substituted aryl, cycloalkyl, and substituted cycloalkyl;and m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen; and

l is an integer from 1 to 7, to produce living protected functionalizedpolymer anions.

Silicone block copolymer anions can then be prepared by anionicallypolymerizing one or more cyclic siloxane monomers of the formula(R¹R²SiO)_(y), wherein R¹ and R² are each independently selected fromthe group consisting of hydrogen, alkyl, substituted alkyl, alkenyl,substituted alkenyl, aryl, and substituted aryl and y=3-10, in an inertsolvent, optionally containing a polymerization promoter, at atemperature from −30° C. to 250° C. for a period of at least one hourwith a protected functionalized living polymer anion as described aboveto provide a living silicone diene and/or alkenylsubstituted aromaticcopolymer anion.

Protonation of the silicone copolymer anion with a suitable protonatingagent, for example acetic acid, affords a protected block copolymer (I):

(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—H  (I).

Capping of the silicone copolymer anion with one or more silicon halidesor alkoxides of the formula (R³R⁴R⁵—Si—X), wherein R³, R⁴ and R⁵ are asdefined above and X is halogen or alkoxide which contain 1-20 carbonatoms, affords a protected copolymer (II):

(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR³R⁴R⁵  (II).

Capping of the silicone copolymer anion with one or more silicon halidesor alkoxides of the formula (R^(3′R) ^(4′)R^(5′)—Si—X), wherein R^(3′),R^(4′) and R^(5′) are as defined and X is halogen or alkoxide whichcontain 1-20 carbon atoms, affords a protected functionalizedmacromonomer (II′):

(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR^(3′)R^(4′)R^(5′)  (II′).

Coupling the living copolymer anion with one or more difunctionalcoupling agents, for example Me₂SiCl₂, affords a protectedhomotelechelic block copolymer (III):

[(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)]₂—L  (III)

in which each —T—(A—R⁷R⁸R⁹)_(m) is the same (and in which example L isSiMe₂), or, alternatively,

a protected heterotelechelic copolymer of formula (III′):

[(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)]₂—L  (III′)

in which each T—(A—R⁷R⁸R⁹)_(m) differs and each C′ can be the same ordifferent. As used herein, the term “heterotelechelic” copolymersinclude polymers in which: each functional group T differs and issimilarly protected (i.e., each —(A—R⁷R⁸R⁹)_(m) is the same); eachfunctional group T is the same and is dissimilarly protected (i.e., each—(A—R⁷R⁸R⁹)_(m) differs); and each functional group T differs and isdissimilarly protected. In this aspect of the invention, theheterotelechelic polymers can be produced by separately polymerizingsiloxane monomers with different protected functionalized livingpolymers as described above to produce different protectedfunctionalized silicone copolymer anions and thereafter linking thedifferent polymer anions using excess linking agent. As will beappreciated by the skilled artisan, the polymer branches can vary inmonomer composition, molecular weight, length, and the like.

The living copolymer anion can be functionalized using a functionalizingagent or electrophile or other material as known in the art to be usefulfor terminating or end capping living polymers to provide protectedheterotelechelic copolymers of formula (III″):

(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—FG  (III″)

in which FG and T—(A—R⁷R⁸R⁹)_(m) differ.

Coupling the living silicon copolymer with one or more multifunctionalcoupling agents, for example SiCl₄, affords a protected radial copolymer(IV):

[(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)]_(z)—L′  (IV).

(in which example L′ is Si and z is 4), in which each T—(A—R⁷R⁸R⁹)_(m)and each C′ can be the same or different. In this regard, when a mixtureof protected functionalized initiators of formula VI or VII above isused, the resultant radial polymer can include arms in which eachfunctional group T differs and is similarly protected; each functionalgroup T is the same and is dissimilarly protected; or each functionalgroup T differs and is dissimilarly protected. In addition, a mixture offunctional and non-functional initiators (such as alkyllithiuminitiators) can also be used to produce radial silicone polymers havingboth functionalized and non-functional arms. The radial polymers can bealso prepared by separately polymerizing siloxane monomers (using thesame or different conjugated diene, alkenylsubstituted aromatic and/orsilicon monomers and/or initiators) to provide living anions, andthereafter linking the living polymer anions with a suitable linkingagent. The resultant radial polymer can include arms or branches ofvarying monomer composition, protected functionality, protecting groups,lengths and molecular weights.

Radial polymers of the formula:

[(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′]_(z)—DVB—[(R¹R²Si—O)_(v)—SiR³R⁴R⁵]_(y)  (V)

in which each T—(A—R⁷R⁸R⁹)_(m) and each C′ can be the same or differentcan be prepared by polymerizing one or more diene and/oralkenylsubstituted aromatic monomers with a protected functionalizedinitiator as described above to form living protected functionalizedpolymer anions; adding at least one alkenylsubstituted aromatic compoundwhich contains two or more independently polymerizable vinyl groups(such as isomeric divinylbenzenes or diisopropenylbenzenes) to theprotected functionalized living polymer anions to form a multi-armliving polymer having a central core; adding one or more siloxanemonomers as described above to grow or polymerize siloxane arms from thecentral core to form a multi-arm living silicone copolymer; and reactingthe multi-arm living silicone copolymer with a capping agent to providea protected functionalized silicone radial copolymer of formula (V).

Novel protected, functionalized silicone triblock copolymers of thepresent invention of the formula X may be prepared as described indetail below.

Protected, functionalized living polymer anions(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—M (XIII) can be prepared by anionicallypolymerizing a conjugated diene, a mixture of conjugated diene monomers,an alkenylsubstituted aromatic compound, a mixture of alkenylsubstitutedaromatic compounds, or a mixture of one or more conjugated dienemonomers together with one or more alkenylsubstituted aromaticcompounds, in an inert solvent, optionally in the presence of a polarmodifier, at a temperature from about −30° C. to about 150° C., for aperiod of at least about one hour, with a protected functionalizedinitiator as described above having the formula:

M—Q_(n)—Z—T—(A—R⁷R⁸R⁹)_(m)  (VI)

or

wherein each of M, Q, n, Z, T, A, R⁷, R⁸, R⁹, R¹ and 1 are as definedabove with regard to the compounds of formula (VI) and (VII).

Silicone block copolymer anions (R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—M (XIV) may then be prepared by anionically polymerizing oneor more cyclic siloxane monomers (R¹R²SiO)_(y) as defined above in aninert solvent, optionally containing a polymerization promoter, at atemperature from about −30° C. to about 250° C., for a period of atleast about one hour, with a protected functionalized living polymeranion (R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—M (XIII).

The resultant silicone copolymer anion (XIV) can be capped with anexcess of a dialkyl or diaryl silicon dihalide of the formulaR¹²R¹³SiX₂, wherein R¹² and R¹³ are as defined above and X is halide,for example dichlorodimethylsilane, to afford a capped protected blockcopolymer (XV):

(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—X  (XV)

Excess dialkyl or diaryl silicon dihalide can be removed.

Living polymer anions R—D—M can be prepared by anionically polymerizingone or more conjugated diene monomers, a mixture of conjugated dienemonomers, one or more alkenylsubstituted aromatic compound, a mixture ofalkenylsubstituted aromatic compounds, or a mixture of one or moreconjugated diene monomers together with one or more alkenylsubstitutedaromatic compounds, in an inert solvent, optionally in the presence of apolar modifier, at a temperature from about −30° C. to about 150° C.,for a period of at least about one hour, with an initiator having theformula:

 R—M

wherein R is a hydrocarbyl group of 1-20 carbon atoms and M is definedas an alkali metal.

Silicone block copolymer anions R—D—(SiR¹⁰R¹¹—O)_(w)—M (XVI) may then beprepared by anionically polymerizing one or more cyclic siloxanemonomers (R¹⁰R¹¹SiO)_(y), wherein R¹⁰, R¹¹ and y are as defined above,in an inert solvent, optionally containing a polymerization promoter, ata temperature from about −30° C. to about 250° C., for a period of atleast about one hour, with a living polymer anion R—D—M.

Coupling the copolymer (XV) with the copolymer anion (XVI) affords theprotected, functionalized triblock copolymer (X):

(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—(O—SiR¹⁰R¹¹)_(w)—D—R  (X).

Alternatively, protected, functionalized triblock copolymers of theformula X may be prepared as described in detail below.

Protected, functionalized living polymer anions of the(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—M (XIII) can be prepared and reacted withone or more cyclic siloxane monomers to form silicone block copolymeranions (R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—M (XIV), as describedabove.

Living polymer anions R—D—M may also be prepared and reacted with one ormore siloxane monomers to form silicone block copolymer anionsR—D—(SiR¹⁰R¹¹—O)_(w)—M (XVI), also as described above. The anions(s) offormula (XVI) may then be capped with an excess of an dialkyl or diarylsilicon dihalide (R¹²R¹³SiX₂) to afford protected block copolymer(XVII):

R—D—(R¹⁰R¹¹Si—O)_(w)—SiR¹²R¹³—X  (XVII)

Excess dialkyl or diaryl silicon dihalide may be removed.

Coupling the copolymer R—D—(R¹⁰R¹¹Si—O)_(w)—SiR¹²R¹³—X (XVII) with thecopolymer anion (R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—M can affordthe protected, functionalized triblock copolymer (X):

(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—(O—SiR¹⁰R¹¹)_(w)—D—R  (X).

Novel protected, functionalized silicone triblock copolymers of thepresent invention of formula XI may be prepared as described in detailbelow.

Protected, functionalized living polymer anions(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)-C′—M (XIII) may be prepared and reacted withone or more siloxane monomers (R¹R²SiO)_(y) to make silicone blockcopolymer anions (R⁷R⁸R⁹A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—M (XIV), allas described above. Capping of the silicone copolymer anion (XIV) withan excess of a dialkyl or diaryl silicon dihalide (R¹²R¹³SiX₂) canafford protected block copolymer (XV):

(R⁷R⁸R⁹A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—X  (XV).

Excess dialkyl or diaryl silicon dihalide (R¹²R¹³SiX₂) may be removed.

Living polymer anions R—D—M may be prepared as described above andcoupled with the protected, functionalized silicone copolymer(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)SiR¹²R¹³—X (XV) to afford theprotected, functionalized silicone triblock copolymer (XI):

(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R ²Si—O)_(v)—SiR¹²R¹³—D—R  (XI).

Alternatively, protected, functionalized triblock copolymers ofstructure XI may be prepared as described in detail below.

Protected, functionalized living polymer anions(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—M (XIII) may be prepared and reacted withone or more siloxane monomers (R¹R²SiO)_(y) to make silicone blockcopolymer anions (R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—M (XIV), asdescribed above. Living polymer anions R—D—M can be prepared asdescribed above and capped with an excess of an dialkyl or diarylsilicon dihalide (R¹²R¹³SiX₂) to afford a polymer R—D—SiR¹²R¹³—X(XVIII). Excess dialkyl or diaryl silicon dihalide may be removed.Coupling the protected, functionalized silicone block copolymer anions(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—M (XIV) with the polymerR—D—SiR¹²R¹³—X (XVIII) affords the copolymer (XI):

(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—D—R  (XI).

Novel protected, functionalized silicone triblock copolymers of thepresent invention such as those having the formula XII may be preparedas described in detail below.

Protected, functionalized living polymer anions(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—M (XIII) and living polymer anions R—D—M maybe prepared as described above. Silicone block copolymer anionsR—D—(SiR¹⁰R¹¹—O)_(w)—M (XVI) may then be prepared by anionicallypolymerizing one or more cyclic siloxane monomers (R¹⁰R¹¹SiO)_(y), witha living polymer anion R—D—M, also as described above. Capping of thesilicone copolymer anion R—D—(SiR¹⁰R¹¹—O)_(w)—M (XVI) with an excess ofa dialkyl or diaryl silicon dihalide (R¹²R¹³SiX₂) can afford protectedblock copolymer (XVII):

R—D—(R¹⁰R¹¹Si—O)_(v)—SiR¹²R¹³—X  (XVII)

Excess dialkyl or diaryl silicon dihalide (R¹²R¹³SiX₂) may be removed.Coupling the copolymer R—D—(R¹⁰R¹¹Si—O)_(v)—SiR¹²R¹³—X (XVII) with thepolymer anion (R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—M (XIII) will afford theprotected, functionalized triblock copolymer (XII):

R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—SiR¹²R¹³—(O—SiR¹⁰R¹¹)_(w)—D—R  (XII).

Alternatively, the protected, functionalized triblock copolymers ofstructure XII may be prepared as described in detail below.

Protected, functionalized living polymer anions(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—M (XIII) may be prepared and cappped with anexcess of a dialkyl or diaryl silicon dihalide R¹²R¹³SiX₂ to affordprotected block polymer (XIX):

(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—SiR¹²R¹³—X  (XIX)

Excess dialkyl or diaryl silicon dihalide may be removed.

Living polymer anions R—D—M may be prepared and reacted with one or morecyclic siloxane monomers (R¹⁰R¹¹SiO)_(y) to make silicone blockcopolymer anions R—D—(SiR¹⁰R¹¹—O)_(w)—M (XVI) as described above.Coupling the polymer (R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—SiR¹²R¹³—X (XIX) withthe copolymer anion R—D—(SiR¹⁰R¹¹—O)_(w)—M (XVI) can afford theprotected, functionalized triblock copolymer (XII):

(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—SiR¹²R¹³—(O—SiR¹⁰R¹¹)_(w)—D—R  (XII)

These procedures efficiently afford terminally protected, functionalizedsilicone block copolymers. The nature of the protected functional groupsor the heteroatom can be varied by merely changing the identity of thefunctional initiator. The number of terminal functional groups can bevaried by merely selecting the appropriate terminating agent or couplingagent.

U.S. Pat. Nos. 5,496,940 and 5,527,753 disclose novel, tertiary aminoinitiators which are soluble in hydrocarbon solvents. These initiators,useful in practicing this invention, are derived fromomega-tertiary-amino-1-haloalkanes of the following general structures:

X—Z—N(A(R¹R²R³))₂

and

wherein: X is halogen, preferably chlorine or bromine; Z is a branchedor straight chain hydrocarbon connecting group which contains 3-25carbon atoms, optionally substituted with aryl or substituted aryl; A isan element selected from Group IVa of the Periodic Table of theElements; R¹, R², and R³ are each independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, aryl, substitutedaryl, cycloalkyl, and substituted cycloalkyl; and m is an integer from 1to 7. The process reacts selected omega-tertiary-amino-1-haloalkaneswhose alkyl groups contain 3 to 25 carbon atoms, with lithium metal at atemperature between about 35° C. and about 130° C., preferably at thereflux temperature of an alkane, cycloalkane, or aromatic reactionsolvent containing 5 to 10 carbon atoms and mixtures of such solvents.

Tertiary amino-1-haloalkanes useful in the practice of this inventioninclude, but are not limited to, 3-(N,N-dimethylamino)- 1-propyl halide,3-(N,N-dimethylamino)-2-methyl-1-propyl halide,3-(N,N-dimethylamino)-2,2-dimethyl 1-propyl halide,4-(N,N-dimethylamino)-1-butyl halide, 5-(N,N-dimethylamino)-1-pentylhalide, 6-(N,N-dimethylamino)-1-hexyl halide,3-(N,N-diethylamino)-1-propyl halide,3-(N,N-diethylamino)-2-methyl-1-propyl halide,3-(N,N-diethylamino)-2,2-dimethyl-1-propyl halide,4-(N,N-diethylamino)-1-butyl halide, 5-(N,N-diethylamino)-1-pentylhalide, 6-(N,N-diethylamino)-1-hexyl halide,3-(N-ethyl-N-methylamino)-1-propyl halide,3-(N-ethyl-N-methylamino)-2-methyl-1-propyl halide,3-(N-ethyl-N-methylamino)-2,2-dimethyl-1-propyl halide,4-(N-ethyl-N-methylamino)-1-butyl halide,5-(N-ethyl-N-methylamino)-1-pentyl halide,6-(N-ethyl-N-methylamino)-1-hexyl halide, 3-(piperidino)-1-propylhalide, 3-(piperidino)-2-methyl-1-propyl halide,3-(piperidino)-2,2-dimethyl-1-propyl halide, 4-(piperidino)-1-butylhalide, 5-(piperidino)-1-pentyl halide, 6-(piperidino)-1-hexyl halide,3-(pyrrolidino)-1-propyl halide, 3-(pyrrolidino)-2-methyl-1-propylhalide, 3-(pyrrolidino)-2,2-dimethyl-1-propyl halide,4-(pyrrolidino)-1-butyl halide, 5-(pyrrolidino)-1-pentyl halide,6-(pyrrolidino)-1-hexyl halide, 3-(hexamethyleneimino)-1-propyl halide,3-(hexamethyleneimino)-2-methyl-1-propyl halide,3-(hexamethyleneimino)-2,2-dimethyl-1-propyl halide,4-(hexamethyleneimino)-1-butyl halide, 5-(hexamethyleneimino)-1-pentylhalide, 6-(hexamethyleneimino)-1-hexyl halide,3-(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane)-1-propyl halide,4-(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane)-1-butyl halide,6-(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane)-1-hexyl halide,3-(N-isopropyl-N-methyl)-1-propyl halide,2-(N-isopropyl-N-methyl)-2-methyl-1-propyl halide,3-(N-isopropyl-N-methyl)-2,2-dimethyl-1-propyl halide, and4-(N-isopropyl-N-methyl)-1-butyl halide. The halo- or halide grouppreferably is chlorine or bromine.

U.S. Pat. No. 5,600,021 discloses novel monofunctional ether initiatorswhich are soluble in hydrocarbon solvents. These initiators, useful inpracticing this invention, are derived fromomega-protected-hydroxy-1-haloalkanes of the following generalstructure:

X—Z—O—(C—R¹R²R³)

wherein: X is halogen, preferably chlorine or bromine; Z is a branchedor straight chain hydrocarbon connecting group which contains 3-25carbon atoms, optionally substituted with aryl or substituted aryl; andR¹, R², and R³ are each independently selected from the group consistingof hydrogen, alkyl, substituted alkyl, aryl, substituted aryl,cycloalkyl, and substituted cycloalkyl. The process reacts selectedomega-hydroxy-protected-1-haloalkanes whose alkyl groups contain 3 to 25carbon atoms, with lithium metal at a temperature between about 35° C.and about 130° C., preferably at the reflux temperature of an alkane,cycloalkane, or aromatic reaction solvent containing 5 to 10 carbonatoms and mixtures of such solvents.

The precursor omega-protected-1-haloalkanes (halides) were prepared fromthe corresponding haloalcohol by the standard literature methods. Forexample, 3-(1,1-dimethylethoxy)-1-chloropropane was synthesized by thereaction of 3-chloro-1-propanol with 2-methylpropene according to themethod of A. Alexakis, M. Gardette, and S. Colin, Tetrahedron Letters,29, 1988, 2951. The method of B. Figadere, X. Franck and A. Cave,Tetrahedron Letters, 34, 1993, 5893, which involved the reaction of theappropriate alcohol with 2-methyl-2-butene catalyzed by borontrifluoride etherate is employed for the preparation of the t-amylethers. The alkoxy, alkylthio or dialkylamino substituted ethers, forexample 6-[3-(methylthio)-1-propyloxy]-1-chlorohexane, were synthesizedby reaction of the corresponding substituted alcohol, for instance3-methylthio-1-propanol, with an alpha-bromo-omega-chloroalkane, forinstance 1-bromo-6-hexane, according to the method of J. Almena, F.Foubelo and M. Yus, Tetrahedron, 51, 1995, 11883. The compound4-(methoxy)-1-chlorobutane, and the higher analogs, were synthesized bythe ring opening reaction of tetrahydrofuran with thionyl chloride andmethanol, according to the procedure of T. Ferrari and P. Vogel,SYNLETT, 1991, 233. The triphenylmethyl protected compounds, for example3-(triphenylmethoxy)-1-chloropropane, are prepared by the reaction ofthe haloalcohol with triphenylmethylchloride, according to the method ofS. K. Chaudhary and O. Hernandez, Tetrahedron Letters, 1979, 95.

Omega-hydroxy-protected-1-haloalkanes useful in practicing thisinvention include, but are not limited to,3-(1,1-dimethylethoxy)-1-propyl halide, 3-(1,1-dimethylethoxy)-2-methyl-1-propyl halide, 3-(1,1-dimethylethoxy)-2,2-dimethyl-1-propyl halide,4-(1,1-dimethylethoxy)-1-butyl halide, 5-(1,1-dimethylethoxy)-1-pentylhalide, 6-(1,1-dimethylethoxy)-1-hexyl halide,8-(1,1-dimethylethoxy)-1-octyl halide, 3-(1,1-dimethylpropoxy)-1-propylhalide, 3-(1,1-dimethylpropoxy)-2-methyl-1-propyl halide,3-(1,1-dimethylpropoxy)-2,2-diemthyl-1-propyl halide,4-(1,1-dimetlylpropoxy)-1-butyl halide, 5-(1,1-dimethylpropoxy)-1-pentylhalide, 6-(1,1-dimethylpropoxy)-1-hexyl halide,8-(1,1-dimethylpropoxy)-1-octyl halide, 4-(methoxy)-1-butyl halide,4-(ethoxy)-1-butyl halide, 4-(propyloxy)-1-butyl halide,4-(1-methylethoxy)-1-butyl halide,3-(triphenylmethoxy)-2,2-dimethyl-1-propyl halide,4-(triphenylmethoxy)-1-butyl halide,3-[3-(dimethylamino)-1-propyloxy]-1-propyl halide,3-[2-(dimethylamino)-1-ethoxy]-1-propyl halide,3-[2-(diethylamino)-1-ethoxy]-1-propyl halide,3-[2-(diisopropyl)amino)-1-ethoxy]-1-propyl halide,3-[2-(1-piperidino)-1-ethoxy]-1-propyl halide,3-[2-(1-pyrrolidino)-1-ethoxy] -1-propyl halide4-[3-(dimethylamino)-1-propyloxy]-1-butyl halide,6-[2-(1-piperidino)-1-ethoxy]-1-hexyl halide,3-[2-(methoxy)-1-ethoxy]-1-propyl halide,3-[2-(ethoxy)-1-ethoxy]-1-propyl halide,4-[2-(methoxy)-1-ethoxy]-1-butyl halide,5-[2-(ethoxy)-1-ethoxy]-1-pentyl halide,3-[3-(methylthio)-1-propyloxy]-1-propyl halide,3-[4-(methylthio)-1-butyloxy]-1-propyl halide,3-(methylthiomethoxy)-1-propyl halide,6-[3-(methylthio)-1-propyloxy]-1-hexyl halide,3-[4-(methoxy)-benzyloxy]-1-propyl halide,3-[4-(1,1-dimethylethoxy)-benzyloxy]-1-propyl halide,3-[2,4-(dimethoxy)-benzyloxy]-1-propyl halide,8-[4-(methoxy)-benzyloxy]-1-octyl halide,4-[4-(methylthio)-benzyloxy]-1-butyl halide,3-[4-(dimethylamino)-benzyloxy]-1-propyl halide,6-[4-(dimethylamino)-benzyloxy]-1-hexyl halide,5-(triphenylmethoxy)-1-pentyl halide, 6-(triphenylmethoxy)-1-hexylhalide, and 8-(triphenylmethoxy)-1-octyl halide. The halo- or halidegroup is preferably chlorine or bromine.

U.S. Pat. No. 5,362,699 discloses novel monofunctional silyl etherinitiators which are soluble in hydrocarbon solvents. These initiators,useful in practicing this invention, are derived fromomega-silyl-protected-hydroxy-1-haloalkanes of the following generalstructure:

X—Z—O—(Si—R¹R²R³)

wherein: X is halogen, preferably chlorine or bromine; Z is a branchedor straight chain hydrocarbon group which contains 3-25 carbon atoms,optionally substituted with aryl or substituted aryl; and R¹, R², and R³are independently defined as saturated and unsaturated aliphatic andaromatic radicals, and their employment as initiators in the anionicpolymerization of olefin containing monomers in an inert, hydrocarbonsolvent optionally containing a Lewis base. The process reacts selectedomega-hydroxy-protected-1-haloalkanes whose alkyl groups contain 3 to 25carbon atoms, with lithium metal at a temperature between about 25 ° C.and about 40 ° C., in an alkane, cycloalkane or aromatic reactionsolvent containing 5 to 10 carbon atoms and mixtures of such solvents.

t-Butyldimethylsilyl protected compounds, for example4-(t-butyldimethylsilyloxy)-1-butylhalide, are prepared fromt-butyldimethylchlorosilane, and the corresponding halo-alcohol,according to the method described in U.S. Pat. No. 5,493,044.Omega-silyloxy-1-haloalkanes prepared in accord with this earlierprocess useful in practicing this invention include, but are not limitedto, 3-(t-butyldimethylsilyloxy)-1-propyl halide,3-(t-butyldimethyl-silyloxy)-2-methyl-1-propyl halide,3-(t-butyldimethylsilyloxy)-2,2-dimethyl-1-propyl halide,4-(t-butyldimethylsilyloxy)-1-butyl halide,5-(t-butyldimethyl-silyloxy)-1-pentyl halide,6-(t-butyldimethylsilyloxy)-1-hexyl halide,8-(t-butyldimethylsilyloxy)-1-octyl halide,3-(t-butyldiphenylylsilyloxy)-1-propyl halide,3-(t-butyldiphenylylsilyloxy)-2-methyl-1-propyl halide,3-(t-butyldiphenylylsilyloxy)-2,2-dimethyl-1-propyl halide,6-(t-butyldimethylsilyloxy)-1-hexyl halide, and3-(trimethylsilyloxy)-2,2-dimethyl-1-propyl halide. The halo- or halidegroup is preferably chlorine or bromine.

Monofunctional thioether initiators useful in the practice of thisinvention are derived from omega-protected-thio-1-haloalkanes of thefollowing general structure:

X—Z—S—(A—R¹R²R³)

wherein: X is halogen, preferably chlorine or bromine; Z is a branchedor straight chain hydrocarbon group which contains 3-25 carbon atoms,optionally substituted with aryl or substituted aryl; (A—R¹R²R³) is aprotecting group in which A is an element selected from Group IVa of thePeriodic Table of the Elements; R¹, R², and R³ are each independentlyselected from the group consisting of hydrogen, alkyl, substitutedalkyl, aryl, substituted aryl, cycloalkyl, and substituted cycloalkyl.The process reacts selected omega-thioprotected-1-haloalkyls whose alkylgroups contain 3 to 25 carbon atoms, with lithium metal at a temperaturebetween about 35 ° C. and about 130° C., preferably at the refluxtemperature of an alkane, cycloalkane or aromatic reaction solventcontaining 5 to 10 carbon atoms and mixtures of such solvents.

The initiator precursor, omega-thio-protected-1-haloalkanes (halides),are prepared from the corresponding halothiol by the standard literaturemethods. For example, 3-(1,1-dimethylethylthio)-1-propylchloride issynthesized by the reaction of 3-chloro-1-propanthiol with2-methylpropene according to the method of A. Alexakis, M. Gardette, andS. Colin, Tetrahedron Letters, 29, 1988, 2951. Alternatively, reactionof 1,1-dimethylethylthiol with 1-bromo-3-chloropropane and a baseaffords 3-(1,1-dimethylethylthio)-1-propylchloride. The method of B.Figadere, X. Franck and A. Cave, Tetrahedron Letters, 34, 1993, 5893,which involved the reaction of the appropriate thiol with2-methyl-2-butene catalyzed by boron trifluoride etherate is employedfor the preparation of the t-amyl thioethers. Additionally,5-(cyclohexylthio)-1-pentylhalide and the like, can be prepared by themethod of J. Almena, F. Foubelo, and M. Yus, Tetrahedron, 51, 1995,11883. This synthesis involves the reaction of the appropriate thiolwith an alkyllithium, then reaction of the lithium salt with thecorresponding alpha, omega dihalide. 3-(Methylthio)-1-propylchloride canbe prepared by chlorination of the corresponding alcohol with thionylchloride, as taught by D. F. Taber and Y. Wang, J. Org, Chem., 58, 1993,6470. Methoxymethylthio compounds, such as6-(methoxymethylthio)-1-hexylchloride, are prepared by the reaction ofthe omega-chloro-thiol with bromochloromethane, methanol, and potassiumhydroxide, by the method of F. D. Toste and I. W. J. Still, Synlett,1995, 159. t-Butyldimethylsilyl protected compounds, for example4-(t-butyldimethylsilylthio)-1-butylhalide, are prepared fromt-butyldimethylchlorosilane, and the corresponding thiol, according tothe method described in U.S. Pat. No. 5,493,044.

Omega-thio-protected 1-haloalkanes prepared in accord with this earlierprocess useful in practicing this invention include, but are not limitedto, 3-(methylthio)-1-propylhalide,3-(methylthio)-2-methyl-1-propylhalide,3-(methylthio)-2,2-dimethyl-1-propylhalide,4-(methylthio)-1-butylhalide, 5-(methylthio)-1-pentylhalide,6-(methylthio)-1-hexylhalide, 8-(methylthio)-1-octylhalide,3-(methoxymethylthio)-1-propylhalide,3-(methoxymethylthio)-2-methyl-1-propylhalide,3-(methoxymethylthio,-2,2-dimethyl-1-propylhalide,4-(methoxymethylthio)-1-butylhalide,5-(methoxymethylthio)-1-pentylhalide,6-(methoxymethylthio)-1-hexylhalide,8-(methoxymethylthio)-1-octylhalide,3-(1,1-dimethylethylthio)-1-propylhalide,3-(1,1-dimethylethylthio)-2-methyl-1-propylhalide,3-(1,1-dimethylethylthio)-2,2-dimethyl-1-propylhalide,4-(1,1-dimethylethylthio)-1-butylhalide,5-(1,1-dimethylethylthio)-1-pentylhalide,6-(1,1-dimethylethylthio)-1-hexylhalide,8-(1,1-dimethylethylthio)-1-octylhalide,3-(1,1-dimethylpropylthio)-1-propylhalide,3-(1,1-dimethylpropylthio)-2-methyl-1-propylhalide,3-(1,1-dimethylpropylthio)-2,2-dimethyl-1-propylhalide,4-(1,1-dimethylpropylthio)-1-butylhalide,5-(1,1-dimethylpropylthio)-1-pentylhalide,6-(1,1-dimethylpropylthio)-1-hexylhalide,8-(1,1-dimethylpropylthio)-1-octylhalide,3-(cyclopentylthio)-1-propylhalide,3-(cyclopentylthio)-2-methyl-1-propylhalide,3-(cyclopentylthio)-2,2-dimethyl-1-propylhalide,4-(cyclopentylthio)-1-butylhalide, 5-(cyclopentylthio)-1-pentylhalide,6-(cyclopentylthio)-1-hexylhalide, 8-(cyclopentylthio)-1-octylhalide,3-(cyclohexylthio)-1-propylhalide,3-(cyclohexylthio)-2-methyl-1-propylhalide,3-(cyclohexylthio)-2,2-dimethyl-1-propylhalide,4-(cyclohexylthio)-1-butylhalide, 5-(cyclohexylthio)-1-pentylhalide,6-(cyclohexylthio)-1-hexylhalide, 8-(cyclohexylthio)-1-octylhalide,3-(t-butyldimethylsilylthio)-1-propylhalide,3-(t-butyldimethylsilylthio)-2-methyl-1-propylhalide,3-(t-butyldimethylsilylthio)-2,2-dimethyl-1-propylhalide,3-(t-butyldimethylsilylthio)-2-methyl-1-propylhalide,4-(t-butyldimethylsilylthio)-1-butylhalide,6-(t-butyldimethylsilylthio)-1-hexylhalide and3-(trimethylsilylthio)-2,2-dimethyl-1-propylhalide. The halo- or halidegroup is preferably chlorine or bromine.

The initiators of the formulae

M—Q_(n)—Z—T—(A—R⁷R⁸R⁹)_(m)  (VI)

or

are prepared by reacting a compound of the formula

M—Z—T—(A—R⁷R⁸R⁹)_(m)  (VIII)

or

wherein M, Z, T, A, R⁷, R⁸, R⁹, R′, m and 1 have the meanings ascribedabove, with one or more conjugated diene hydrocarbons, one or morealkenylsubstituted aromatic compounds, or mixtures of one or more dieneswith one or more alkenylsubstituted aromatic compounds, to form anextended hydrocarbon chain between M and Z in formulas (VIII) and (IX),which extended chain is denoted as Q_(n)in formulas (VI) and (VII). Thecompounds of formula(VIII) and (IX) are prepared by first, reacting inan inert solvent a selected tertiary amino-1-haloalkane or anomega-hydroxy-protected-1-haloalkane or anomega-thio-protected-1-haloalkane, depending on whether “T” is to be N,O or S (the alkyl portions of the haloalkyl groups contain 3 to 25carbon atoms) with an alkali metal, preferably lithium, at a temperaturebetween about 35° C. and about 130° C., preferably at the solvent refluxtemperature, to form a protected monofunctional lithium initiator (offormula VIII or IX), which is then optionally reacted with one or moreconjugated diene hydrocarbons, one or more alkenylsubstituted aromaticcompounds, or mixtures of one or more dienes with one or morealkenylsubstituted aromatic compounds, in a predominantly alkane,cycloalkane, or aromatic reaction solvent, or mixture thereof, whichsolvent contains 5 to 10 carbon atoms, and mixtures of such solvents toproduce a monofunctional initiator with an extended chain or tetherbetween the metal atom (M) and element (T) in formula (VI) and (VII)above and mixtures thereof with compounds of Formula (VIII) and/or (IX).

Thus, incorporation of Q groups into the M—Z linkage to form thecompounds of formulas (VI) and (VII) above involves addition ofcompounds of the formula

M—Z—T—(A—R⁷R⁸R⁹)_(m)  (VIII)

or

where the symbols have the meanings ascribed above, across the carbon tocarbon double bonds in compounds selected from the group consisting ofone or more conjugated diene hydrocarbons, one or morealkenylsubstituted aromatic compounds, or mixtures of one or more dieneswith one or more alkenylsubstituted aromatic compounds to produce newcarbon-lithium bonds of an allylic or benzylic nature, similar to thosefound in a propagating polyalkadiene or polyarylethylene polymer chainderived by anionic initiation of the polymerization of conjugated dienesor arylethylenes. These new carbon-lithium bonds are now “activated”toward polymerization and so are much more efficient in promotingpolymerization than the precursor M—Z (M═Li) bonds, themselves.

Suitable conjugated dienes to produce the chain extended initiatorpreferably contain from 4 to 12, more preferably from 4 to 8, carbonatoms per molecule. Examples of these compounds include withoutlimitation 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene,1,3-pentadiene, myrcene, 2-methyl-3-ethyl-1,3-butadiene,2-methyl-3-ethyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-hexadiene,1,3-heptadiene, 3-methyl-1,3-heptadiene, 1,3-octadiene,3-butyl-1,3-octadiene, 3,4-dimethyl-1,3-hexadiene,3-n-propyl-1,3-pentadiene, 4,5-diethyl-1,3-octadiene,2,4-diethyl-1,3-butadiene, 2,3-di-n-propyl-1,3-butadiene,2-methyl-3-isopropyl-1,3-butadiene, and the like and mixtures thereof.Among the dialkylbutadienes, it is preferred that the alkyl groupscontain from 1 to 3 carbon atoms.

Suitable alkenylsubstituted aromatic compounds to produce the chainextended initiator include without limitation styrene,alpha-methylstyrene, vinyltoluene, 2-vinylpyridine, 4-vinylpyridine,1-vinylraphthalene, 2-vinylnaphthalene, 1-alpha-methylvinylnaphthalene,2-alpha-methylvinylnaphathalene, 1,2-diphenyl-4-methylhexene-1 and thelike and mixtures of these, as well as alkyl, cycloalkyl, aryl, alkaryland aralkyl derivatives thereof in which the total number of carbonatoms in the combined hydrocarbon constituents is generally not greaterthan 18. Examples of these latter compounds include without limitation3-methylstyrene, 3,5-diethylstyrene, 4-(tert-butyl)-styrene,2-ethyl-4-benzylstyrene, 4-phenylstyrene, 4-p-tolylstyrene,2,4-divinyltoluene, 4,5-dimethyl-1-vinylnaphthalene, and the like andmixtures thereof. Reference is made to U.S. Pat. No. 3,377,404 fordisclosures of additional vinyl-substituted aromatic compounds.Non-polymerizable alkenyl substituted aromatic compounds such as1,1-diphenylethylene may also be used.

The hydrocarbon monomer to be polymerized is selected from the group ofconjugated alkadienes, such as butadiene and isoprene, andalkenylsubstituted aromatic compounds, such as styrene andalpha-methylstyrene. The hydrocarbon monomers may be polymerized alone,or in admixture with each other to form random copolymers, or bycharging the monomers to the reaction mixture sequentially to form blockcopolymers. Examples of conjugated diene hydrocarbons include, but arenot limited to, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene,1,3-pentadiene, myrcene, 2-methyl-3-ethyl-1,3-butadiele,2-methyl-3-ethyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-hexadiene,1,3-heptadiene, 3-methyl-1,3-heptadiene, 1,3-octadiene,3-butyl-1,3-octadiene, 3,4-dimethyl-1,3-hexadiene,3-n-propyl-1,3-pentadiene, 4,5-diethyl-1,3-octadiene,2,4-diethyl-1,3-butadiene, 2,3-di-n-propyl-1,3-butadiene, and2-methyl-3-isopropyl-1,3-butadiene, and the like and mixtures thereof.Examples of polymerizable alkenylsubstituted aromatic compounds whichcan be anionically polymerized include, but are not limited to, styrene,alpha-methylstyrene, vinyltoluene, 2-vinylpyridine, 4-vinylpyridine,1-vinylnaphthalene, 2-vinylnaphthalene, 1-alpha-methylvinylnaphthalene,2-alpha-methylvinylnaphathalene, 1,2-diphenyl-4-methyl-1-hexene, and thelike, and mixtures of these, as well as alkyl, cycloalkyl, aryl, alkaryland aralkyl derivatives thereof in which the total number of carbonatoms in the combined hydrocarbon constituents is generally not greaterthan 18. Examples of these latter compounds include 3-methylstyrene,3,5-diethylstyrene, 2-ethyl-4-benzylstyrene, 4-phenylstyrene,4-p-tolylstyrene, 2,4-divinyltoluene and4,5-dimethyl-1-vinylnaphthalene. Again, reference is made to U.S. Pat.No. 3,377,404 for disclosures of additional alkenylsubstituted aromaticcompounds.

The inert solvent employed during the polymerizations is preferably anon-polar solvent such as a hydrocarbon, since anionic polymerization inthe presence of such non-polar solvents is known to produce polyeneswith high 1,4-contents from 1,3-dienes. Inert hydrocarbon solventsuseful in practicing this invention include but are not limited to inertliquid alkanes, cycloalkanes and aromatic solvents and mixtures thereof.Exemplary alkanes and cycloalkanes include those containing five to 10carbon atoms, such as pentane, hexane, cyclohexane, methylcyclohexane,heptane, methylcycloheptane, octane, decane and the like and mixturesthereof. Exemplary aryl solvents include those containing six to tencarbon atoms, such as toluene, ethylbenzene, p-xylene, m-xylene,o-xylene, n-propylbenzene, isopropylbenzene, n-butylbenzene, and thelike and mixtures thereof.

Polar solvents (modifiers) can be added to the hydrocarbonpolymerization reaction to alter the microstructure of the resultingpolymer, i.e., increase the proportion of 1,2 (vinyl) microstructure orto promote functionalization or randomization. Examples of polarmodifiers include, but are not limited to, diethyl ether, dibutyl ether,tetrahydrofuran, 2-methyltetrahydrofuran, methyl tert-butyl ether,1,2-dimethoxyethane (glyme), 1,2-diethoxyethane,diazabicyclo[2.2.2]octane, triethylamine, tributylamine,N-methylpiperidine, N-methylpyrrolidine, N,N,N′,N′-tetramethylethylenediamine (TMEDA), and the like, and mixtures thereof. The amount of thepolar modifier added depends on the vinyl content desired, the nature ofthe monomer, the temperature of the polymerization, and the identity ofthe polar modifier. The polar solvent (modifier) can be added to thereaction medium at the beginning of the polymerization as part of thesolvent reaction medium or added during the polymerization.

Examples of silicone monomers (R¹R²SiO)_(y) and (R¹⁰R¹¹SiO)_(y) include,but are not limited to, (Me₂SiO)₃, (MeHSiO)₃, (Me₂SiO)₄, (Me₂SiO)₅,(MeHSiO)₄, (MeHSiO)₅, (Ph₂SiO)₃, (Ph₂SiO)₄, (Ph₂SiO)₅, (PhHSiO)₃,(PhHSiO)₄, (PhHSiO)₅, (vinylHSiO)₃, (vinylHSiO)₄, (vinylHSiO)₅,(vinylMeSiO)₃, (vinylMeSiO)₄, (vinylMeSiO)₅, (PhMeSiO)₃, (PhMeSiO)₄,(PhMeSiO)₅, and the like and mixtures thereof.

Examples of capping or terminating agents of the formula(R^(3′)R^(4′)R^(5′)—Si—X) useful for the preparation of functionalizedmacromonomers, include, but are not limited to,chloro-(3-methacryloxypropyl)dimethylsilane,(3-methacryloxypropyl)trimethoxysilane,chloro-(2-methacryloxyethyl)-dimethylsilane,chloro-(2-acryloxyethyl)dimethylsilane,chloro-dimethyl-4-vinylphenylsilane, chlorodimethyl-2-vinylphenylsilane,epihalohydrins, such as epichlorohydrin, and the like and mixturesthereof.

Examples of capping or terminating agents of the formula (R³R⁴R⁵—Si—X)include, but are not limited to, Me₃Si—Cl, t-ButylMe₂Si—Cl, Et₃Si—Cl,Me₂PhSi—Cl, Me₂vinylSi—Cl, Et₃Si—OMe, Et₃Si—OEt,1H,1H,2H,2H-perfluorodecyldimethyl-chlorosilane (see U.S. Pat. No.5,486,568), CH₃CH₂OCHCH₃OCH₂CH₂CH₂SiMe₂OPh (see U.S. Pat. No.5,478,899), Me₃Si—Br, Me₂vinylSi—OMe, Me₂PhSi—OMe, and the like andmixtures thereof.

Examples of difunctional coupling agents useful in forming protectedhomotelechelic and heterotelechelic silicone polymers include, but arenot limited to, Me₂SiCl₂, Me₂Si(OMe)₂, Me₂SnCl₂, Ph₂SiCl₂, MePhSiCl₂,ClMe₂SiCH₂CH₂SiMe₂Cl, Me₂SiBr₂, and the like and mixtures thereof.

Examples of multifunctional coupling agents include, but are not limitedto, SiCl₄, SnCl₄, MeSiCl₃, HSi(OMe)₃, Si(OEt)₄, Cl₃SiSiCl₃, and the likeand mixtures thereof.

Examples of silicone polymerization promoters include, but are notlimited to, tetrahydrofuran (THF), N,N,N′,N-tetramethylethylene diamine(TMEDA), 1,2-dipipieridinoethane (DPE), dimethylsulfoxide (DMSO),N,N,N′,N-tetraethylethylene diamine (TEEDA), 1,2-dimethoxyethane (DME),and the like and mixtures thereof.

Non-functionalized initiators capable of initiating polymerization ofconjugated dienes or alkenylsubstituted aromatic compounds useful in thepractice of this invention are represented by the formula R—M, wherein Mis an alkali metal selected from lithium, sodium and potassium; and Rrepresents an aliphatic, cycloaliphatic, or arylsubstituted aliphaticradical. Preferably, R is an alkyl or substituted alkyl group of 1-20carbon atoms. Such initiators include, but are not limited to,methyllithium, ethyllithium, n-propyllithium, 2-propyllithium,n-butyllithium, s-butyllithium, t-butyllithium, isobutyllithium,n-hexyllithium, n-octyllithium, 2-ethylhexyllithium,2-(cyclohexyl)ethyllithium, and the like, and mixtures thereof.

Electrophiles that are useful in functionalizing the polymeric livinganion include, but are not limited to, haloalkyltrialkoxysilanes,alkenylhalosilanes and omega-alkenylarylhalosilanes, such aschlorotrimethylsilane and styrenyldimethyl chlorosilane; allyl halides,such as allyl bromide and allyl chloride; epihalohydrins, such asepichlorohydrin, epibromohydrin, and epiiodohydrin, and other materialsas known in the art to be useful for terminating or end capping siliconpolymers. The only proviso is that the initiator and the electrophilecontain different functional groups, thus leading to hetero-telechelicpolymers. The functionalizing step can be conducted at temperaturesranging from about −30° C. to about 150° C.

Examples of methods to hydrogenate the polymers of this invention aredescribed in U.S. Pat. Nos. 4,970,254, 5,166,277, 5,393,843 and5,496,898. The hydrogenation of the functionalized polymer is conductedin situ, or in a suitable solvent, such as hexane, cyclohexane, orheptane. This solution is contacted with hydrogen gas in the presence ofa catalyst, such as a nickel catalyst. The hydrogenation is typicallyperformed at temperatures from 25° C. to 150° C., with a archetypalhydrogen pressure of 15 psig to 1000 psig. The progress of thishydrogenation can be monitored by InfraRed (IR) spectroscopy or NuclearMagnetic Resonance (NMR) spectroscopy. The hydrogenation reaction isconducted until at least 90% of the aliphatic unsaturation has beensaturated. The hydrogenated functional polymer is then recovered byconventional procedures, such as removal of the catalyst with aqueousacid wash, followed by solvent removal or precipitation of the polymer.

If desired, the protecting groups can be removed from the siliconecopolymer. This deprotection can be performed either prior to or afterthe optional hydrogenation of the residual aliphatic unsaturation. Forexample, to remove tert-alkyl-protected groups, the protected polymer ismixed with Amberlyst® 15 ion exchange resin and heated at an elevatedtemperature, for example 150° C., until deprotection is complete. Inaddition, tert-alkyl-protected groups can also be removed by reaction ofthe polymer with trifluoroacetic acid, p-toluenesulfonic acid ortrimethylsilyliodide. Additional methods of deprotection of thetert-alkyl protecting groups can be found in T. W. Greene and P. G. M.Wuts, Protective Groups in Organic Synthesis, Second Edition, Wiley, NewYork, 1991, page 41.

The tert-butyldimethylsilyl protecting groups can be removed bytreatment of the polymer cement with acid, such as hydrochloric acid,acetic acid, paratoluensulfonic acid, or Dowex® 50W-X8. Alternatively, asource of fluoride ions, for instance tetra-n-butylammonium fluoride,potassium fluoride and 18-crown-6, or pyridine-hydrofluoric acidcomplex, can be employed for deprotection of the tert-butyldimethylsilylprotecting groups. Additional methods of deprotection of thetert-butyldimethylsilyl protecting groups can be found in T. W. Greeneand P. G. M. Wuts, Protective Groups in Organic Synthesis, SecondEdition, Wiley, New York, 1991, pages 80-83. If desired, the protectinggroups can be selectively removed from the polymer in the presence ofeach other either prior to or after the optional hydrogenation of theresidual aliphatic unsaturation.

The following table details experimental conditions that willselectively remove one of the protecting groups (more labile) from thepolymer, while retaining the other protecting group (more stable).

LABILE STABLE CONDITIONS t-Butyldimethylsilyl Acetal Tetrabutylammoniumfluoride t-Butyldimethylsilyl Ketal Tetrabutylammonium fluoridet-Butyldimethylsilyl Orthoester Tetrabutylammonium fluoridet-Butyldimethylsilyl Aminal Tetrabutylammonium fluoride Acetal t-Butyl 1N HCl Ketal t-Butyl 1 N HCl Orthoester t-Butyl 1 N HCl Aminal t-Butyl 1N HCl Acetal Dialkylamino 1 N HCl Ketal Dialkylamino 1 N HCl OrthoesterDialkylamino 1 N HCl Aminal Dialkylamino 1 N HCl2,2,5,5-Tetramethyl-2,5- Acetal Tetrabutylammoniumdisila-1-azacyclopentane Fluoride 2,2,5,5-Tetramethyl-2,5- KetalTetrabutylammonium disila-1-azacyclopentane Fluoride2,2,5,5-Tetramethyl-2,5- Orthoester Tetrabutylammoniumdisila-1-azacyclopentane Fluoride 2,2,5,5-Tetramethyl-2,5- AminalTetrabutylammonium disila-1-azacyclopentane Fluoride

Deprotection of copolymer (I) affords a functionalized siliconecopolymer with the structure:

(H)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—H

wherein T, Z, Q, C′, R¹, R², m, n, and v are as defined above.Deprotection of copolymer (II) affords a functionalized siliconecopolymer with the structure:

(H)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR³R⁴R⁵

wherein T, Z, Q, C′, R¹, R², R³, R⁴, R⁵, m, n, and v are as definedabove. Deprotection of copolymer (II′) affords a functionalized siliconemacromonomer with the structure:

(H)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR^(3′)R^(4′)R^(5′)

wherein T, Z, Q, C′, R¹, R², R^(3′), R^(4′), R^(5′), m, n, and v are asdefined above. Deprotection of copolymer (III) affords a functionalizedhomotelechelic silicone copolymer with the structure:

[(H)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)]₂—L

wherein T, Z, Q, C′, R¹, R², L, m, n, and v are as defined above.

Deprotection of copolymer (III′) affords a functionalizedheterotelechelic silicone copolymer with the structure:

[(H)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)]₂—L

in which T, Z, Q, C′, R², R³, L, m, n, and v are as defined above, withthe proviso that each T is different.

Deprotection of copolymer (III″) affords a functionalizedheterotelechelic silicone copolymer with the structure:

(H)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—FG

in which T, Z, Q, C′, R¹, R², FG, m, n, and v are as defined above, withthe proviso that each T is different.

As the skilled artisan will appreciate, a heterotelechelic copolymer(III′) or (III″) having different protecting groups can be selectivelydeprotected to remove one but not the other of the protecting groups.This allows the ability to perform additional chemistries at theliberated functional groups (such as copolymerization to form polymersegments or modification of the functional groups to a differentfunctionality, as described in more detail below), followed optionallyby deprotection and additional chemistries of the remaining protectedfunctional group.

Deprotection of copolymer (IV) and (V) affords functionalized radialcopolymers with the following structures:

[(H)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)]_(z)—L′

or

[(H)_(m)—T—Z—Q_(n)—C′]_(z)—DVB—[(R¹R²Si—O)_(v)—SiR³R⁴R⁵]_(y)

in which T, Z, Q, C′, DVB, R¹, R², R³, R⁴, R⁵, L′, m, n, v, y and z areas defined above. Similar to the heterotelechelic copolymers, for radialcopolymers (IV) and (V) having differently protected functional groupsT, the functional groups can be selectively deprotected to remove onebut not the other of the protecting groups, additional chemistriesperformed at the liberated functional groups, followed optionally bydeprotection and additional chemistries of the remaining protectedfunctional groups.

Deprotection of copolymers (X), (XI), and (XII) affords functionalizedsilicone copolymers with the following structures, respectively:

(H)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—(O—SiR¹⁰R¹¹)_(w)—D—R

(H)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—D—R

and

(H)_(m)—T—Z—Q_(n)—C′—SiR¹²R¹³—(O—SiR¹⁰R¹¹)_(w)—D—R

wherein T, Z, Q, C′, D, R, R¹, R², R¹⁰, R¹¹, R¹², R¹³, m, n, v and w areas defined above.

As discussed above, the polymers of the invention can be deprotected,and the polymers can optionally be reacted with one or more comonomersto polymerize a functional end thereof. Protecting groups can be removedsimultaneously or sequentially. For example, the polymers can be reactedwith one or more comonomers in the presence of a strong acid catalyst tosimultaneously deprotect the functional polymer and polymerize thefunctional end thereof to produce novel segmented block polymers.Alternatively, differently protected functional groups can beselectively deprotected to remove one but not the other of theprotecting groups, additional chemistries performed at the liberatedfunctional groups, followed optionally by deprotection and additionalchemistries of the remaining protected functional groups.

Exemplary comonomers include without limitation cyclic ethers, diamines,diisocyanates, polyisocyanates, di-, poly- and cyclic amides, di- andpolycarboxylic acids, diols, polyols, anhydrides, and th, like andmixtures thereof. For example, functionalized copolymers can be furtherreacted with monofunctional monomers, such as caprolactam, or otherlactams, to form a polyamide block polymer segment, or cyclic etherssuch ethylene oxide to form polyether blocks; or with difunctionalmonomers, such as diacids or anhydrides and diamines to form polyamideblocks, or diacids or anhydrides or lactones and diols to form polyesterblocks, or diols and polyols with diisocyanates or polyisocyanates toform polyurethane blocks. Polyisocyanates or polyfunctional polyols areexamples of polyfunctional monomers. The functional group may also bereacted with a suitable agent containing a reactive olefinic bond, suchas a styrenic or acrylic functionality, such as methacroyl chloride,which will act to change the nature of the functionality and provide a“macromonomer” capable of polymerizing with other free radicallypolymerizable monomers.

The present invention will be further illustrated by the followingnon-limiting examples.

EXAMPLE 1 Preparation ofAlpha-(t-Butoxy)-Omega-Trimethsilyloxy-Block-Polyisoprene-Block-Poly(dimethylsiloxane)

A 250 ml glass reactor is equipped with four break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. 3-(1,1-Dimethylethoxy)-1-propyllithium (chain extended withtwo equivalents of isoprene) 16.0 wt. % in cyclohexane, 0.516 grams (2.0mmoles) is added to the reactor with a syringe via the inlet tube.Cyclohexane, 100 ml, is then vacuum distilled directly into the reactor.The flask is then removed from the vacuum line by a flame seal.Isoprene, 20.00 grams (294 mmole) is then added from a break-sealampoule. The reaction mixture is stirred at room temperature for twelvehours to complete the polymerization. An aliquot is withdrawn with asyringe through the sample port, quenched with degassed methanol, andexamined by SEC, and has the following properties:

M_(n)=1.00×10⁴ g/mole

M_(w)=1.04×10⁴ g/mole

M_(w)/M_(n)=1.04.

Sublimed hexamethylcyclotrisiloxane, 12.0 grams (53.9 mmole), isdissolved in cyclohexane (20 ml) and this solution is added from one ofthe break seal ampoules. Dry tetrahydrofuran, 20 ml, is then added fromanother ampoule. The reaction mixture is then placed in a constanttemperature bath at 40° C. After eight hours, the conversion is about90%. Excess chlorotrimethylsilane, 1.09 grams (10.0 mmole) is then addedto terminate the polymerization, added from the last break-seal ampoule.The functionalized polymer is recovered by precipitation two times intomethanol, and vacuum dried for twenty four hours.

The resultant functionalized silicone polymer is characterized by ¹H NMRand SEC, and has the following properties:

M_(n)=1.60×10⁴ g/mole

M_(w)=1.70×10⁴ g/mole

M_(w)/M_(n)=1.06.

The ¹H NMR spectrum exhibits a peak at 1.17 ppm for the t-butoxy group.No cyclic oligomer is detected by SEC analysis.

EXAMPLE 2 Preparation ofAlpha-(2,2,5,5-Tetramethyl-2,5-Disila-1-Azacyclopentyl)-Omega-(3-Methacryloxypropyl)-dimethylsilyl-Block-Polyisoprene-Block-Poly(methylphenylsiloxane)

A 250 ml glass reactor is equipped with four break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature.3-(2,2,5,5-Tetramethyl-2,5-disila-1-azacyclopentane)-1-propyllithium12.0 wt. % in cyclohexane, 0.725 grams (3.5 mmoles) is added to thereactor with a syringe via the inlet tube. Cyclohexane, 100 ml, is thenvacuum distilled directly into the reactor. The flask is then removedfrom the vacuum line by a flame seal. Isoprene, 21.00 grams (308.3mmole) is then added from a break-seal ampoule. The reaction mixture isstirred at room temperature for twelve hours to complete thepolymerization. An aliquot is withdrawn with a syringe through thesample port, quenched with degassed methanol, and examined by SEC, andhas the following properties:

M_(n)=6.00×10³ g/mole

M_(w)=6.24×10³ g/mole

M_(w)/M_(n)=1.04.

Methylphenylcyclotrisiloxane, 21.0 grams (51.4 mmole), is dissolved incyclohexane (20 ml) and this solution is added from one of the ampoules.Dry tetrahydrofuran, 20 ml, is then added from another ampoule. Thereaction mixture is then placed in a constant temperature bath at 40° C.After eight hours, the conversion is about 90%. The polymerizationreaction is terminated with 3.09 grams (14 mmole) ofchloro-(3-methacryloxypropyl)-dimethylsilane, added from the lastbreak-seal ampoule. The functionalized polymer is recovered byprecipitation two times into methanol, and is vacuum dried for twentyfour hours.

The resultant functionalized silicone polymer is characterized by ¹H NMRand SEC, and has the following properties:

M_(n)=1.20×10⁴ g/mole

M_(w)=1.30×10⁴ g/mole

M_(w)/M_(n)=1.08.

No cyclic oligomer is detected by SEC analysis.

The NMR clearly exhibits the signals characteristic of the methacrylgroup.

EXAMPLE 3 Preparation ofAlpha-Amino-Omega-(3-Methacryloxypropyl)-dimethylsilyl-Block-Polyisoprene-Block-Poly(methylphenylsiloxane)

A 100 ml, flask is fitted with a magnetic stir bar, a reflux condenser,and a nitrogen inlet. This apparatus is dried in an oven overnight at125° C., assembled hot, and allowed to cool in a stream of nitrogen. Theprotected amine functionalized silicone polymer, prepared in Example 2,(1.00 gram), tetrahydrofuran (10 ml) and 1N HCl (1 ml) are added to theflask. The reaction mixture is heated to reflux. The progress of thereaction is monitored by TLC, for disappearance of the startingmaterial. Once all the starting material had been consumed, the reactionmixture is allowed to cool to room temperature. After solvent removal,the resultant polymer cement is precipitated into methanol and is vacuumdried.

The resultant functionalized silicone polymer is characterized by ¹H NMRand SEC, and has the following properties:

M_(n)=1.20×10⁴ g/mole

M_(w)=1.30×10⁴ g/mole

M_(w)/M_(n)=1.08.

The NMR clearly exhibits the signals characteristic of the methacrylgroup.

EXAMPLE 4 Preparation of ABA TriblockTelechelic-(t-Butyldimethylsilyloxy)-Block-Polybutadiene-Block-Poly(dimethylsiloxane)

A 250 ml glass reactor is equipped with four break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. 3-(t-Butyldimethylsilyloxy)-1-propyllithium 18.0 wt. % incyclohexane, 0.901 grams (5.0 mmoles) is added to the reactor with asyringe via the inlet tube. Cyclohexane, 100 ml, is then vacuumdistilled directly into the reactor. The flask is then removed from thevacuum line by a flame seal. Butadiene, 25.00 grams (430.7 mmole) isthen added from a break-seal ampoule. The reaction mixture is stirred atroom temperature for sixteen hours to complete the polymerization. Analiquot is withdrawn with a syringe through the sample port, quenchedwith degassed methanol, and examined by SEC, and has the followingproperties:

M_(n)=5.00×10³ g/mole

M_(w)=5.15×10³ g/mole

M_(w)/M_(n)=1.03.

Sublimed hexamethylcyclotrisiloxane, 50.0 grams (224.7 mmole), isdissolved in cyclohexane (20 ml) and this solution is added from one ofthe break seal ampoules. Dry tetrahydrofuran, 20 ml, and anhydrousN,N-dimethylacetamide, 1.0 ml, is then added from another ampoule. Thereaction mixture is then placed in a constant temperature bath at 40° C.After eight hours, the conversion is about 90%. Excessdichlorodimethylsilane, 1.94 grams (15.0 mmole) is then added toterminate the polymerization, added from the last break-seal ampoule.The functionalized polymer is recovered by precipitation two times intomethanol, and vacuum dried for twenty four hours.

The resultant functionalized silicone polymer is characterized by ¹H NMRand SEC, and has the following properties:

M_(n)=2.00×10⁴ g/mole

M_(w)=2.12×10⁴ g/mole

M_(w)M_(n)=1.06.

The ¹H NMR spectrum exhibits a peak at 0.88 ppm for thet-butyldimethylsilyloxy group, No cyclic oligomer is detected by SECanalysis.

EXAMPLE 5 Preparation ofAlpha-(t-Butoxy)-Omega-Trimethsilyloxy-Block-Polyisoprene-Block-Poly(dimethylsiloxane)

A 250 mt. glass reactor is equipped with four break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. 3-(1,1-Dimethylethoxy)-1-propyllithium (chain extended withtwo equivalents of isoprene) 16.0 wt. % in cyclohexane, 0.516 grams (2.0mmoles) is added to the reactor with a syringe via the inlet tube.Cyclohexane, 100 ml., is then vacuum distilled directly into thereactor. The flask is then removed from the vacuum line by a flame seal.Isoprene, 20.00 grams (294 mmole) is then added from a break-sealampoule. The reaction mixture is stirred at room temperature for twelvehours to complete the polymerization. An aliquot is withdrawn with asyringe through the sample port, quenched with degassed methanol, andexamined by SEC, and has the following properties:

M_(n)=1.00×10⁴ g/mole

M_(w)32 1.04×10⁴ g/mole

M_(w)/M_(n)=1.04

Sublimed hexamethylcyclotrisiloxane, 12.0 grams (53.9 mmole), isdissolved in cyclohexane (20 ml.) and this solution is added from one ofthe break seal ampoules. Dry tetrahydrofuiran, 20 ml., is then addedfrom another ampoule. The reaction mixture is then placed in a constanttemperature bath at 40° C. After eight hours, the conversion is about90%. Excess chlorotrimethylsilane, 1.09 grams (10.0 mmole) is then addedto terminate the polymerization, added from the last break-seal ampoule.The functionalized polymer is recovered by precipitation two times intomethanol, and vacuum dried for twenty four hours.

The resultant functionalized silicone polymer is characterized by ¹H NMRand SEC, and has the following properties:

M_(n)=1.60×10⁴ g/mole

M_(w)=1.70×10⁴ g/mole

M_(w)/M_(n)=1.06

The ¹HNMR spectrum exhibits a peak at 1.17 ppm for the t-butoxy group.No cyclic oligomer is detected by SEC analysis.

EXAMPLE 6 Preparation ofAlpha-(2,2,5,5-Tetramethyl-2,5-Disila-1-Azacyclopentyl)-Omega-(3-Methacryloxypropyl)-dimethylsilyl-Block-Polyisoprene-Block-Poly(methylphenylsiloxane)

A 250 ml. glass reactor is equipped with four break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature.3-(2,2,5,5-Tetramethyl-2,5-disila-1-azacyclopentane)-1-propyllithium12.0 wt. % in cyclohexane, 0.725 grams (3.5 mmoles) is added to thereactor with a syringe via the inlet tube. Cyclohexane, 100 ml., is thenvacuum distilled directly into the reactor. The flask is then removedfrom the vacuum line by a flame seal. Isoprene, 21.00 grams (308.3mmole) is then added from a break-seal ampoule. The reaction mixture isstirred at room temperature for twelve hours to complete thepolymerization. An aliquot is withdrawn with a syringe through thesample port, quenched with degassed methanol, and examined by SEC, andhas the following properties:

M_(n)=6.00×10³ g/mole

M_(w)=6.24×10³ g/mole

M_(w)/M_(n)=1.04

Methylphenylcyclotrisiloxane, 21.0 grams (51.4 mmole), is dissolved incyclohexane (20 ml.) and this solution is added from one of theampoules. Dry tetrahydrofuran, 20 ml., is then added from anotherampoule. The reaction mixture is then placed in a constant temperaturebath at 40° C. After eight hours, the conversion is about 90%. Thepolymerization reaction is terminated with 3.09 grams (14 mmole) ofchloro-(3-methacryloxypropyl)-dimethylsilane, added from the lastbreak-seal ampoule. The functionalized polymer is recovered byprecipitation two times into methanol, and is vacuum dried for twentyfour hours.

The resultant functionalized silicone polymer is characterized by ¹HNMRand SEC, and has the following properties:

M_(n)=1.20×10⁴ g/mole

M_(w)=1.30×10⁴ g/mole

M_(w)/M_(n)=1.08

No cyclic oligomer is detected by SEC analysis.

The NMR clearly exhibits the signals characteristic of the methacrylgroup.

EXAMPLE 7 Preparation ofAlpha-Amino-Omega-(3-Methacryloxypropyl)-dimethylsilyl-Block-Polyisoprene-Block-Poly(methylphenylsiloxane)

A 100 ml., flask is fitted with a magnetic stir bar, a reflux condenser,and a nitrogen inlet. This apparatus is dried in an oven overnight at125° C., assembled hot, and allowed to cool in a stream of nitrogen. Theprotected amine functionalized silicone polymer, prepared in Example 2,(1.00 gram), tetrahydrofuran (10 ml) and 1 N HCl (1 ml.) are added tothe flask. The reaction mixture is heated to reflux. The progress of thereaction is monitored by TLC, for disappearance of the startingmaterial. Once all the starting material had been consumed, the reactionmixture is allowed to cool to room temperature. After solvent removal,the resultant polymer cement is precipitated into methanol and is vacuumdried.

The resultant functionalized silicone polymer is characterized by ¹HNMRand SEC, and has the following properties:

M_(n)=1.20×10⁴ g/mole

M_(w)=1.30×10⁴ g/mole

M_(w)/M_(n)=1.08

The NMR clearly exhibits the signals characteristic of the methacrylgroup.

EXAMPLE 8 Preparation of ABA TriblockTelechelic-(t-Butyldimethylsilyloxy)-Block-Polybutadiene-Block-Poly(dimethylsiloxane)

A 250 ml. glass reactor is equipped with four break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. 3-(t-Butyldimethylsilyloxy)-1-propyllithium 18.0 wt. % incyclohexane, 0.901 grams (5.0 mmoles) is added to the reactor with asyringe via the inlet tube. Cyclohexane, 100 ml., is then vacuumdistilled directly into the reactor. The flask is then removed from thevacuum line by a flame seal. Butadiene, 25.00 grams (430.7 mmole) isthen added from a break-seal ampoule. The reaction mixture is stirred atroom temperature for sixteen hours to complete the polymerization. Analiquot is withdrawn with a syringe through the sample port, quenchedwith degassed methanol, and examined by SEC, and has the followingproperties:

M_(n)=5.00×10³ g/mole

M_(w)=5.15×10³ g/mole

M_(w)/M_(n)=1.03

Sublimed hexamethylcyclotrisiloxane, 50.0 grams (224.7 mmole), isdissolved in cyclohexane (20 ml.) and this solution is added from one ofthe break seal ampoules. Dry tetrahydrofuran, 20 ml., and anhydrousN,N-dimethylacetamide, 1.0 ml, is then added from another ampoule. Thereaction mixture is then placed in a constant temperature bath at 40° C.After eight hours, the conversion is about 90%. Excessdichlorodimethylsilane, 1.94 grams (15.0 mmole) is then added toterminate the polymerization, added from the last break-seal ampoule.The functionalized polymer is recovered by precipitation two times intomethanol, and vacuum dried for twenty four hours.

The resultant functionalized silicone polymer is characterized by ¹HNMRand SEC, and has the following properties:

M_(n)=2.00×10⁴ g/mole

M_(w)=2.12×10⁴ g/mole

M_(w)/M_(n)=1.06

The ¹HNMR spectrum exhibits a peak at 0.88 ppm for thet-butyldimethylsilyloxy group.

No cyclic oligomer is detected by SEC analysis.

The foregoing examples are illustrative of the present invention and arenot to be construed as limiting thereof. The invention is defined by thefollowing claims, with equivalents of the claims to be included therein.

That which is claimed is:
 1. Protected functionalized triblock siliconeblock copolymers selected from the group consisting of:(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—(O—SiR¹⁰R¹¹)_(w)—D—R  (X),(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—D—R  (XI) and(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—SiR¹²R¹³—(O—SiR¹⁰R¹¹)_(w)—D—R  (XII)wherein: each Q is independently selected from an unsaturated orhydrogenated hydrocarbyl group derived by incorporation of one or moreconjugated diene hydrocarbons, one or more alkenylsubstituted aromaticcompounds, or a mixture of one or more dienes with one or morealkenylsubstituted aromatic compounds; each n is independently aninteger from 0 to 5; each Z is independently selected from a branched orstraight chain hydrocarbon connecting group which contains 3-25 carbonatoms, optionally substituted with aryl or substituted aryl; each C′ andD is independently selected from a hydrogenated or unsaturated blockderived by anionic polymerization of one or more conjugated dienes, oneor more alkenylsubstituted aromatic compounds, or a mixture of one ormore conjugated dienes and one or more alkenylsubstituted aromaticcompounds; each T is independently selected from the group consisting ofoxygen, sulfur, and nitrogen groups and mixtures thereof; each(A—R⁷R⁸R⁹)_(m) is independently a protecting group in which A is anelement selected from Group IVa of the Periodic Table of the Elements;R⁷, R⁸, and R⁹ are each independently selected from the group consistingof hydrogen, alkyl, substituted alkyl, aryl, substituted aryl,cycloalkyl and substituted cycloalkyl or when T is nitrogen, each R⁹ isoptionally a —(CR′R′)_(l)-group linking two A wherein each R′ is eachindependently selected from the group consisting of hydrogen, alkyl,substituted alkyl, aryl, substituted aryl, cycloalkyl, and substitutedcycloalkyl, and l is an integer from 1 to 7; and m is 1 when T is oxygenor sulfur, and 2 when T is nitrogen; each R¹, R², R¹⁰, R¹¹, R¹², and R¹³is independently selected from the group consisting of hydrogen, alkyl,substituted alkyl, alkenyl, substituted alkenyl, aryl, and substitutedaryl; each R is independently selected from a hydrocarbyl group of 1-20carbon atoms derived from an unfunctionalized initiator capable ofinitiating polymerization of conjugated dienes or alkenyl substitutedaromatic compounds; and each w and v is independently selected from aninteger from 2 to 100,000.
 2. The protected functionalized siliconecopolymer of claim 1, wherein said copolymer comprises a compound of theformula(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—(O—SiR¹⁰R¹¹)_(w)—D—R  (X).3. The protected functionalized silicone copolymer of claim 1, whereinsaid copolymer comprises a compound of the formula(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—D—R  (XI).
 4. Theprotected functionalized silicone copolymer of claim 1, wherein saidcopolymer comprises a compound of the formula(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—SiR¹²R¹³—(O—SiR¹⁰R¹¹)_(w)—D—R  (XII).
 5. Theprotected functionalized silicone copolymer of claim 1, wherein A iscarbon.
 6. The protected functionalized silicone copolymer of claim 1,wherein A is silicon.
 7. A process for the preparation of protectedfunctionalized silicone diene and alkenylsubstituted aromaticcopolymers, comprising the steps of: (1) anionically polymerizing one ormore conjugated diene monomers, a mixture of conjugated diene monomers,one or more alkenylsubstituted aromatic compounds, a mixture ofalkenylsubstituted aromatic compounds, or a mixture of one or moreconjugated diene monomers together with one or more alkenylsubstitutedaromatic compounds, in an inert solvent, optionally in the presence of apolar modifier, at a temperature from about −30° C. to about 150° C.,for a period of at least about one hour, with a protected functionalizedinitiator having the formula: M—Q_(n)—Z—T—(A—R⁷R⁸R⁹)_(m)  (VI) wherein:M is an alkali metal; Q is an unsaturated or hydrogenated hydrocarbylgroup derived by incorporation of one or more conjugated dienehydrocarbons, one or more alkenylsubstituted aromatic compounds, or amixture of one or more conjugated dienes with one or morealkenylsubstituted aromatic compounds; Z is a branched or straight chainhydrocarbon connecting group which contains 3-25 carbon atoms,optionally substituted with aryl or substituted aryl; T is selected fromthe group consisting of oxygen, sulfur, and nitrogen groups and mixturesthereof; (A—R⁷R⁸R⁹)_(m) is a protecting group in which A is an elementselected from Group IVa of the Periodic Table of the Elements, R⁷, R⁸,and R⁹ are independently selected from the group consisting of hydrogen,alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl andsubstituted cycloalkyl, or when T is nitrogen, each R⁹ is optionally a—(CR′R′)_(l)-group linking two A wherein each R′ is each independentlyselected from the group consisting of hydrogen, alkyl, substitutedalkyl, aryl, substituted aryl, cycloalkyl, and substituted cycloalkyl,and l is an integer from 1 to 7; and m is 1 when T is oxygen or sulfur,and 2 when T is nitrogen; and n is an integer from 0 to 5; to produce atleast one protected, functionalized living polymer anion of the formula(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—M, wherein C′ is a hydrogenated orunsaturated block derived by anionic polymerization of one or moreconjugated dienes, one or more alkenylsubstituted aromatic compounds, ora mixture of one or more conjugated dienes and one or morealkenylsubstituted aromatic compounds; (2) anionically polymerizing oneor more conjugated diene monomers, a mixture of conjugated dienemonomers, one or more alkenylsubstituted aromatic compounds, a mixtureof alkenylsubstituted aromatic compounds, or a mixture of one or moreconjugated diene monomers together with one or more alkenylsubstitutedaromatic compounds, in an inert solvent, optionally in the presence of apolar modifier, at a temperature from about −30° C. to about 150° C.,for a period of at least about one hour, with an initiator having theformula R—M, wherein R is a hydrocarbyl group of 1-20 carbon atoms and Mis an alkali metal, to produce at least one non-functionalized livingpolymer anion R—D—M, wherein D is a hydrogenated or unsaturated blockderived by anionic polymerization of one or more conjugated dienes, oneor more alkenylsubstituted aromatic compounds, or a mixture of one ormore conjugated dienes and one or more alkenylsubstituted aromaticcompounds; (3) reacting said protected functionalized living polymeranion of (1), or said non-functionalized living polymer anion of (2), orboth, with one or more siloxane monomers to form at least one siliconeblock living copolymer anion; (4) capping at least one of said protectedfunctionalized living polymer anion of (1), said non-functionalizedliving polymer anion of (2) or said silicone block living copolymeranion of (3) with one or more dialkyl or diaryl silicon dihalidesilicone capping agents to form at least one polymer capped with areactive halogen; and (5) coupling at least one of said capped polymersof (4) with one of said protected functionalized living polymer anion of(1), said non-functionalized living polymer anion of (2), or saidsilicone block living copolymer anion of (3).
 8. The process of claim 7,wherein step (3) comprises reacting said protected funtionalized livingpolymer anion of (1).
 9. The process of claim 7, wherein step (3)comprises reacting said non-functionalized living polymer anion of (2).10. The process of claim 7, wherein step (3) comprises reacting saidprotected functionalized living polymer anion of (1) and saidnon-functionalized living polymer anion of (2).
 11. The process of claim7, wherein step (4) comprises capping said protected functionalizedliving polymer anion of (1).
 12. The process of claim 7, wherein step(4) comprises capping said non-functionalized living polymer anion of(2).
 13. The process of claim 7, wherein step (4) comprises capping saidsilicone block living copolymer anion of (3).
 14. A process for thepreparation of protected functionalized silicone diene andalkenylsubstituted aromatic copolymers, comprising the steps of:anionically polymerizing one or more conjugated diene monomers, amixture of conjugated diene monomers, one or more alkenylsubstitutedaromatic compounds, a mixture of alkenylsubstituted aromatic compounds,or a mixture of one or more conjugated diene monomers together with oneor more alkenylsubstituted aromatic compounds, in an inert solvent,optionally in the presence of a polar modifier, at a temperature fromabout −30° C. to about 150° C., for a period of at least about one hour,with a protected functionalized initiator having the formula:M—Q_(n)—Z—T—(A—R⁷R⁸R⁹)_(m)  (VI) wherein: M is an alkali metal; Q is anunsaturated or hydrogenated hydrocarbyl group derived by incorporationof one or more conjugated diene hydrocarbons, one or morealkenylsubstituted aromatic compounds, or a mixture of one or moreconjugated dienes with one or more alkenylsubstituted aromaticcompounds; Z is a branched or straight chain hydrocarbon connectinggroup which contains 3-25 carbon atoms, optionally substituted with arylor substituted aryl; T is selected from the group consisting of oxygen,sulfur, and nitrogen groups and mixtures thereof; (A—R⁷R⁸R⁹)_(m) is aprotecting group in which A is an element selected from Group Iva of thePeriodic Table of the Elements, R⁷, R⁸, and R⁹ are independentlyselected from the group consisting of hydrogen, alkyl, substitutedalkyl, aryl, substituted aryl, cycloalkyl and substituted cycloalkyl, orwhen T is nitrogen, each R⁹ is optionally a —(CR′R′)_(l)-group linkingtwo A wherein each R′ is each independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, aryl, substitutedaryl, cycloalkyl, and substituted cycloalkyl, and l is an integer from 1to 7; and m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen;and n is an integer from 0 to 5; to produce at least one protected,functionalized living polymer anion of the formula(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—M, wherein C′ is a hydrogenated orunsaturated block derived by anionic polymerization of one or moreconjugated dienes, one or more alkenylsubstituted aromatic compounds, ora mixture of one or more conjugated dienes and one or morealkenylsubstituted aromatic compounds; anionically polymerizing one ormore cyclic siloxane monomers (R¹R²SiO)_(y) wherein each R¹ and R² isindependently selected from the group consisting of hydrogen, alkyl,substituted alkyl, alkenyl, substituted alkenyl, aryl, and substitutedaryl and y=3-10, in an inert solvent, optionally containing apolymerization promoter, at a temperature from about −30° C. to about250° C., for a period of at least about one hour, with said protectedfunctionalized living polymer anion (R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—M toform one or more silicone block copolymer anions of the formula(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—M, wherein v is an integerfrom 2 to 100,000; anionically polymerizing one or more conjugated dienemonomers, a mixture of conjugated diene monomers, one or morealkenylsubstituted aromatic compounds, a mixture of alkenylsubstitutedaromatic compounds, or a mixture of one or more conjugated dienemonomers together with one or more alkenylsubstituted aromaticcompounds, in an inert solvent, optionally in the presence of a polarmodifier, at a temperature from about −30° C. to about 150° C., for aperiod of at least about one hour, with an initiator having the formulaR—M, wherein R is a hydrocarbyl group of 1-20 carbon atoms and M is analkali metal, to produce at least one non-functionalized living polymeranion R—D—M, wherein D is a hydrogenated or unsaturated block derived byanionic polymerization of one or more conjugated dienes, one or morealkenylsubstituted aromatic compounds, or a mixture of one or moreconjugated dienes and one or more alkenylsubstituted aromatic compounds;anionically polymerizing one or more cyclic siloxane monomers(R¹⁰R¹¹SiO)_(y), wherein each R¹⁰ and R¹¹ is independently selected fromthe group consisting of hydrogen, alkyl, substituted alkyl, alkenyl,substituted alkenyl, aryl, and substituted aryl and y=3-10, in an inertsolvent, optionally containing a polymerization promoter, at atemperature from about −30° C. to about 250° C., for a period of atleast about one hour, with said living polymer anion R—D—M to form oneor more silicone block copolymer anions of the formulaR—D—(SiR¹⁰R¹¹—O)_(w)—M, wherein w is an integer from 2 to 100,000;capping at least one of said silicone block copolymer anions of theformula (R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)-C′—(R¹R²Si—O)_(v)—M or of the formulaR—D—(SiR¹⁰R¹¹—O)_(w)—M with a dialkyl or diaryl silicon dihalide of theformula R¹²R¹³SiX₂, wherein R¹² and R¹³ are each independently selectedfrom the group consisting of hydrogen, alkyl, substituted alkyl,alkenyl, substituted alkenyl, aryl, and substituted aryl and X ishalide, to form a halogen capped protected block copolymer(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—X orR—D—(SiR¹⁰R¹¹—O)_(w)—SiR¹²R¹³—X; and coupling at least one of saidcapped copolymers with one of said silicone block copolymer anion(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—M or said silicone blockcopolymer anion R—D—(SiR¹⁰R¹¹—O)_(w)—M.
 15. The process of claim 14,wherein: said capping step comprises reacting said silicone blockcopolymer anion of the formula(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—M with said dialkyl or diarylsilicon dihalide R¹²R¹³SiX₂ to make a capped polymer of the formula(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³ 13 X; and saidcoupling step comprises coupling said capped polymer(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—X with said siliconeblock copolymer anion R—D—(SiR¹⁰R¹¹—O)_(w)—M to make a polymer of theformula(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—(O—SiR¹⁰R¹¹)_(w)—D—R.16. The process of claim 14, wherein: said capping step comprisesreacting said silicone block copolymer anion of the formulaR—D—(SiR¹⁰R¹¹—O)_(w)—M with said dialkyl or diaryl silicon dihalideR¹²R¹³SiX₂ to make a capped polymer of the formulaR—D—(R¹⁰R¹¹Si—O)_(w)—SiR¹²R¹³—X; and said coupling step comprisescoupling said capped polymer R—D—(R¹⁰R¹¹Si—O)_(w)—SiR¹²R¹³—X with saidsilicone block copolymer anion(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—M to make a polymer of theformula(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—(O—SiR¹⁰R¹¹)_(w)—D—R.17. The process of claim 14, further comprising: removing at least oneprotecting group (A—R⁷R⁸R⁹)_(m) to liberate at least one functionalgroup T; and optionally reacting said liberated functional group T withone or more comonomers to produce a polymer segment.
 18. The process ofclaim 17, wherein said removing step and said reacting step occursimultaneously.
 19. The process of claim 14, further comprising:removing at least one protecting group (A—R⁷R⁸R⁹)_(m) to liberate atleast one functional group T; and optionally reacting said liberatedfunctional group T under conditions sufficient to modify thefunctionality of T to incorporate a reactive olefinic bond.
 20. Theprocess of claim 14, further comprising the step of hydrogenating saidcapped copolymer coupled with one of said silicone block copolymer anion(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—M or said silicone blockcopolymer anion R—D—(SiR¹⁰R¹¹—O)_(w)—M.
 21. A process for thepreparation of protected functionalized silicone diene andalkenylsubstituted aromatic copolymers, comprising the steps of:anionically polymerizing one or more conjugated diene monomers, amixture of conjugated diene monomers, one or more alkenylsubstitutedaromatic compounds, a mixture of alkenylsubstituted aromatic compounds,or a mixture of one or more conjugated diene monomers together with oneor more alkenylsubstituted aromatic compounds, in an inert solvent,optionally in the presence of a polar modifier, at a temperature fromabout −30° C. to about 150° C., for a period of at least about one hour,with a protected functionalized initiator having the formula:M—Q_(n)—Z—T—(A—R⁷R⁸R⁹)_(m)  (VI) wherein: M is an alkali metal; Q is anunsaturated or hydrogenated hydrocarbyl group derived by incorporationof one or more conjugated diene hydrocarbons, one or morealkenylsubstituted aromatic compounds, or a mixture of one or moreconjugated dienes with one or more alkenylsubstituted aromaticcompounds; Z is a branched or straight chain hydrocarbon connectinggroup which contains 3-25 carbon atoms, optionally substituted with arylor substituted aryl; T is selected from the group consisting of oxygen,sulfur, and nitrogen groups and mixtures thereof; (A—R⁷R⁸R⁹)_(m) is aprotecting group in which A is an element selected from Group IVa of thePeriodic Table of the Elements, R⁷, R⁵, and R⁸ are independentlyselected from the group consisting of hydrogen, alkyl, substitutedalkyl, aryl, substituted aryl, cycloalkyl and substituted cycloalkyl, orwhen T is nitrogen, each R⁹ is optionally a —(CR′R′)_(l)-group linkingtwo A wherein each R′ is each independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, aryl, substitutedaryl, cycloalkyl, and substituted cycloalkyl, and l is an integer from 1to 7; and m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen;and n is an integer from 0 to 5; to produce at least one protected,functionalized living polymer anion of the formula(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—M, wherein C′ is a hydrogenated orunsaturated block derived by anionic polymerization of one or moreconjugated dienes, one or more alkenylsubstituted aromatic compounds, ora mixture of one or more conjugated dienes and one or morealkenylsubstituted aromatic compounds; anionically polymerizing one ormore cyclic siloxane monomers (R¹R²SiO)_(y) wherein each R¹ and R² isindependently selected from the group consisting of hydrogen, alkyl,substituted alkyl, alkenyl, substituted alkenyl, aryl, and substitutedaryl and y=3-10, in an inert solvent, optionally containing apolymerization promoter, at a temperature from about −30° C. to about250° C., for a period of at least about one hour, with said protectedfunctionalized living polymer anion (R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—M toform one or more silicone block copolymer anions of the formula(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—M, wherein v is an integerfrom 2 to 100,000; anionically polymerizing one or more conjugated dienemonomers, a mixture of conjugated diene monomers, one or morealkenylsubstituted aromatic compounds, a mixture of alkenylsubstitutedaromatic compounds, or a mixture of one or more conjugated dienemonomers together with one or more alkenylsubstituted aromaticcompounds, in an inert solvent, optionally in the presence of a polarmodifier, at a temperature from about −30° C. to about 150° C., for aperiod of at least about one hour, with an initiator having the formulaR—M, wherein R is a hydrocarbyl group of 1-20 carbon atoms and M is analkali metal, to produce at least one non-functionalized living polymeranion R—D—M, wherein D is a hydrogenated or unsaturated block derived byanionic polymerization of one or more conjugated dienes, one or morealkenylsubstituted aromatic compounds, or a mixture of one or moreconjugated dienes and one or more alkenylsubstituted aromatic compounds;capping at least one of said silicone block copolymer anion of theformula (R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—M or saidnon-functionalized living polymer anion of the formula R—D—M with adialkyl or diaryl silicon dihalide of the formula R¹²R¹³SiX₂, whereinR¹² and R¹³ are each independently selected from the group consisting ofhydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl,and substituted aryl and X is halide, to form a halogen capped polymerof the formula (R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—X orR—D—SiR¹²R¹³—X; and coupling at least one of said capped polymers withat least one of said non-functionalized living polymer anion R—D—M orsaid silicone block copolymer anion of the formula(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—M.
 22. The process of claim21, wherein: said capping step comprises reacting said silicone blockcopolymer anion of the formula(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—M with said dialkyl or diarylsilicon dihalide R¹²R¹³SiX₂ to make a capped polymer of the formula(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—X; and said couplingstep comprises coupling said capped polymer(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—X with saidnon-functionalized living polymer anion R—D—M to make a polymer of theformula (R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—D—R.
 23. Theprocess of claim 21, wherein: said capping step comprises reacting saidnon-functionalized living polymer anion of the formula R—D—M with saiddialkyl or diaryl silicon dihalide R¹²R¹³SiX₂ to make a capped polymerof the formula R—D—SiR¹²R¹³—X; and said coupling step comprises couplingsaid capped polymer R—D—SiR²R¹—X with said silicone block copolymeranion (R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—M to make a polymer ofthe formula (R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—D—R. 24.The process of claim 21, further comprising: removing at least oneprotecting group (A—R⁷R⁸R⁹)_(m) to liberate at least one functionalgroup T; and optionally reacting said liberated functional group T withone or more comonomers to produce a polymer segment.
 25. The process ofclaim 24, wherein said removing step and said reacting step occursimultaneously.
 26. The process of claim 21, further comprising:removing at least one protecting group (A—R⁷R⁸R⁹)_(m) to liberate atleast one functional group T; and optionally reacting said liberatedfunctional group T under conditions sufficient to modify thefunctionality of T to incorporate a reactive olefinic bond.
 27. Theprocess of claim 21, further comprising the step of hydrogenating saidcapped polymer coupled with one of said non-functionalized livingpolymer anion R—D—M or said silicone block copolymer anion of theformula (R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—M.
 28. A process forthe preparation of protected functionalized silicone diene andalkenylsubstituted aromatic copolymers, comprising the steps of:anionically polymerizing one or more conjugated diene monomers, amixture of conjugated diene monomers, one or more alkenylsubstitutedaromatic compounds, a mixture of alkenylsubstituted aromatic compounds,or a mixture of one or more conjugated diene monomers together with oneor more alkenylsubstituted aromatic compounds, in an inert solvent,optionally in the presence of a polar modifier, at a temperature fromabout −30° C. to about 150° C., for a period of at least about one hour,with a protected functionalized initiator having the formula:M—Q_(n)—Z—T—(A—R⁷R⁸R⁹)_(m)  (VI) wherein: M is an alkali metal; Q is anunsaturated or hydrogenated hydrocarbyl group derived by incorporationof one or more conjugated diene hydrocarbons, one or morealkenylsubstituted aromatic compounds, or a mixture of one or moreconjugated dienes with one or more alkenylsubstituted aromaticcompounds; Z is a branched or straight chain hydrocarbon connectinggroup which contains 3-25 carbon atoms, optionally substituted with arylor substituted aryl; T is selected from the group consisting of oxygen,sulfur, and nitrogen groups and mixtures thereof; (A—R⁷R⁸R⁹)_(m) is aprotecting group in which A is an element selected from Group IVa of thePeriodic Table of the Elements, R⁷, R⁸, and R⁹ are independentlyselected from the group consisting of hydrogen, alkyl, substitutedalkyl, aryl, substituted aryl, cycloalkyl and substituted cycloalkyl, orwhen T is nitrogen, each R⁹ is optionally a —(CR′R′)_(l)-group linkingtwo A wherein each R′ is each independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, aryl, substitutedaryl, cycloalkyl, and substituted cycloalkyl, and l is an integer from 1to 7; and m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen;and n is an integer from 0 to 5; to produce at least one protected,functionalized living polymer anion of the formula(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—M, wherein C′ is a hydrogenated orunsaturated block derived by anionic polymerization of one or moreconjugated dienes, one or more alkenylsubstituted aromatic compounds, ora mixture of one or more conjugated dienes and one or morealkenylsubstituted aromatic compounds; anionically polymerizing one ormore conjugated diene monomers, a mixture of conjugated diene monomers,one or more alkenylsubstituted aromatic compounds, a mixture ofalkenylsubstituted aromatic compounds, or a mixture of one or moreconjugated diene monomers together with one or more alkenylsubstitutedaromatic compounds, in an inert solvent, optionally in the presence of apolar modifier, at a temperature from about −30° C. to about 150° C.,for a period of at least about one hour, with an initiator having theformula R—M, wherein R is a hydrocarbyl group of 1-20 carbon atoms and Mis an alkali metal, to produce at least one non-functionalized livingpolymer anion R—D—M, wherein D is a hydrogenated or unsaturated blockderived by anionic polymerization of one or more conjugated dienes, oneor more alkenylsubstituted aromatic compounds, or a mixture of one ormore conjugated dienes and one or more alkenylsubstituted aromaticcompounds; anionically polymerizing one or more cyclic siloxane monomers(R¹⁰R¹¹SiO)_(y), wherein each R¹⁰ and R¹¹ is independently selected fromthe group consisting of hydrogen, alkyl, substituted alkyl, alkenyl,substituted alkenyl, aryl, and substituted aryl and y=3-10, in an inertsolvent, optionally containing a polymerization promoter, at atemperature from about −30° C. to about 250° C., for a period of atleast about one hour, with said living polymer anion R—D—M to form oneor more silicone block copolymer anions of the formulaR—D—(SiR¹⁰R¹¹—O)_(w)—M, wherein w is an integer from 2 to 100,000;capping at least one of said protected functionalized polymer anion ofthe formula (R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—M or said silicone blockcopolymer anion of the formula R—D—(SiR¹⁰R¹¹—O)_(w)—M with a dialkyl ordiaryl silicon dihalide of the formula R¹²R¹³SiX₂, wherein R¹² and R¹³are each independently selected from the group consisting of hydrogen,alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, andsubstituted aryl and X is halide, to form a halogen capped polymer(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—SiR¹²R¹³—X orR—D—(SiR¹⁰R¹¹—O)_(w)—SiR¹²R¹³—X; and coupling at least one of saidcapped polymers with at least one of said protected functionalizedliving polymer anion of the formula (R⁷R⁸R⁹—A)m—T—Z—Q_(n)—C′—M or saidsilicone block copolymer of the formula R—D—(SiR¹⁰R¹¹—O)_(w)—M.
 29. Theprocess of claim 28, wherein: said capping step comprises reacting saidprotected functionalized living polymer anion of the formula(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—M with said dialkyl or diaryl silicondihalide R¹²R¹³SiX₂ to make a capped polymer of the formula(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—SiR¹²R¹³—X; and said coupling step comprisescoupling said capped polymer (R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—SiR¹²R¹³—X withsaid silicone block copolymer anion R—D—(SiR¹⁰R¹¹—O)_(w)—M to make apolymer of the formula(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—SiR¹⁰R¹¹—(O—SiR¹⁰R¹¹)_(w)—D—R.
 30. Theprocess of claim 28, wherein: said capping step comprises reacting saidsilicone block copolymer anion of the formula R—D—(SiR¹⁰R¹¹—O)_(w)—Mwith said dialkyl or diaryl silicon dihalide R¹²R¹³SiX₂ to make a cappedpolymer of the formula R—D—(R¹⁰R¹¹Si—O)_(w)—SiR¹²R¹³—X; and saidcoupling step comprises coupling said capped polymerR—D—(R¹⁰R¹¹Si—O)_(w)—SiR¹²R¹³—X with said protected functionalizedliving polymer anion (R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—M to make a polymer ofthe formula (R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—SiR¹²R¹³—(O—SiR¹⁰R¹¹)_(w)—D—R.31. The process of claim 28, further comprising: removing at least oneprotecting group (A—R⁷R⁸R⁹)_(m) to liberate at least one functionalgroup T; and optionally reacting said liberated functional group T withone or more comonomers to produce a polymer segment.
 32. The process ofclaim 31, wherein said removing step and said reacting step occursimultaneously.
 33. The process of claim 28, further comprising:removing at least one protecting group (A—R⁷R⁸R⁹)_(m) to liberate atleast one functional group T; and optionally reacting said liberatedfunctional group T under conditions sufficient to modify thefunctionality of T to incorporate a reactive olefinic bond.
 34. Theprocess of claim 28, further comprising the step of hydrogenating saidcapped copolymer coupled with at least one of said protectedfunctionalized living polymer anion of the formula(R⁷R⁸R⁹—A)_(m)—T—Z—Q_(n)—C′—M or said silicone block copolymer of theformula R—D—(SiR¹⁰R¹¹—O)_(w)—M.
 35. A functionalized silicone diene oralkenylsubstituted aromatic copolymer selected from the group consistingof: (H)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—(O—SiR¹⁰R¹¹)_(w)—D—R,(H)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—D—R and(H)_(m)—T—Z—Q_(n)—C′—SiR¹²R¹³—(O—SiR¹⁰R¹¹)_(w)—D—R wherein: each Q isindependently selected from an unsaturated or hydrogenated hydrocarbylgroup derived by incorporation of one or more conjugated dienehydrocarbons, one or more alkenylsubstituted aromatic compounds, or amixture of one or more dienes with one or more alkenylsubstitutedaromatic compounds; each n is independently an integer from 0 to 5; eachZ is independently selected from a branched or straight chainhydrocarbon connecting group which contains 3-25 carbon atoms,optionally substituted with aryl or substituted aryl; each C′ and D isindependently selected from a hydrogenated or unsaturated block derivedby anionic polymerization of one or more conjugated dienes, one or morealkenylsubstituted aromatic compounds, or a mixture of one or moreconjugated dienes and one or more alkenylsubstituted aromatic compounds;each T is independently selected from the group consisting of oxygen,sulfur, and nitrogen groups and mixtures thereof; m is 1 or 2; each R¹,R², R¹⁰, R¹¹, R¹², and R¹³ is independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, alkenyl, substitutedalkenyl, aryl, and substituted aryl; each R is independently selectedfrom a hydrocarbyl group of 1-20 carbon atoms derived from anunfunctionalized initiator capable of initiating polymerization ofconjugated dienes or alkenyl substituted aromatic compounds; and each wand v is independently selected from an integer from 2 to 100,000. 36.The functionalized silicone copolymer of claim 35, wherein saidcopolymer comprises a compound of the formula(H)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—(O—SiR¹⁰R¹¹)_(w)—D—R. 37.The functionalized silicone copolymer of claim 35, wherein saidcopolymer comprises a compound of the formula(H)_(m)—T—Z—Q_(n)—C′—(R¹R²Si—O)_(v)—SiR¹²R¹³—D—R.
 38. The functionalizedsilicone copolymer of claim 35, wherein said copolymer comprises acompound of the formula(H)_(m)—T—Z—Q_(n)—C′—SiR¹²R¹³—(O—SiR¹⁰R¹¹)_(w)—D—R.